Methods of Making Fused Ring Compounds

ABSTRACT

The present invention relates to methods of making fused ring compounds, such as indeno-fused naphthols, and fused ring indenopyran compounds, such as indeno-fused naphthopyrans, that each employ an unsaturated compound represented by the following Formula II. 
     
       
         
         
             
             
         
       
     
     Referring to the unsaturated compound of Formula II: Ring-A can be selected from optionally substituted aryl (e.g., phenyl); m can be, for example, from 0 to 4; R 1  for each m can be selected from optionally substituted hydrocarbyl (e.g., C 1 -C 6  alkyl) optionally interrupted with at least one linking group (e.g., —O—); and R 3  and R 16  can each be independently selected from, for example, hydrogen or optionally substituted hydrocarbyl, such as C 1 -C 8  alkyl. When Ring-A is a phenyl group, the unsaturated compound represented by Formula II can be referred to as an unsaturated indanone acid/ester compound, or an indenone acid/ester compound (depending on whether R 16  is hydrogen, or an optionally substituted hydrocarbyl group).

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.15/344,919, filed Nov. 7, 2016, now U.S. Pat. No. 9,878,971, issued Jan.30, 2018, which is a divisional of U.S. application Ser. No. 14/822,938,filed Aug. 11, 2015, now U.S. Pat. No. 9,487,499, issued Nov. 8, 2016,which is a divisional of U.S. application Ser. No. 13/314,735, filedDec. 8, 2011, now U.S. Pat. No. 9,139,571, issued Sep. 22, 2015, whichclaims the benefit of U.S. Provisional Application No. 61/459,613, filedon Dec. 16, 2010, all of which are incorporated herein by reference intheir entirety.

FIELD OF THE INVENTION

The present invention relates to methods of making fused ring compoundsand fused ring indenopyran compounds that each involve the use ofcertain unsaturated compounds.

BACKGROUND OF THE INVENTION

Indeno-fused ring compounds, such as A and B ring fused inden-6-olcompounds, have many uses, such as intermediates in the synthesis ofphotochromic compounds and materials, such as indeno-fused ring pyrancompounds, including A and B ring fused indenopyran compounds.Photochromic materials, such as indeno-fused naphthopyrans, in responseto certain wavelengths of electromagnetic radiation (or “actinicradiation”), typically undergo a transformation from one form or stateto another form, with each form having a characteristic ordistinguishable absorption spectrum associated therewith. Typically,upon exposure to actinic radiation, many photochromic materials aretransformed from a closed-form, which corresponds to an unactivated (orbleached, e.g., substantially colorless) state of the photochromicmaterial, to an open-form, which corresponds to an activated (orcolored) state of the photochromic material. In the absence of exposureto actinic radiation, such photochromic materials are reversiblytransformed from the activated (or colored) state, back to theunactivated (or bleached) state. Compositions and articles, such aseyewear lenses, that contain photochromic materials or have photochromicmaterials applied thereto (e.g., in form of a photochromic coatingcomposition) typically display colorless (e.g., clear) and coloredstates that correspond to the colorless and colored states of thephotochromic materials contained therein or applied thereto.

Indeno-fused naphthol materials such as A and B ring fused inden-6-olcompounds are typically prepared by a synthetic scheme involving thereaction of a benzophenone with a dialkyl succinate, which is typicallyreferred to as a Stobbe reaction route. When unsymmetrical benzophenonesare used, a mixture of indeno-fused naphthol materials typically resultsfrom the Stobbe reaction route. The mixture of indeno-fused naphtholstypically must be separated so as to isolate the desired indeno-fusednaphthol. The isolated indeno-fused naphthol can then be used insubsequent reactions (e.g., in the synthesis of photochromicindeno-fused naphthopyrans). The separation and isolation stepsgenerally result in significantly reduced yields relative to the desiredindeno-fused naphthol materials.

Some photochromic materials, such as photochromic indeno-fusednaphthopyrans can be expensive, and in light of economic considerations,reducing the costs associated with synthesizing such materials istypically desirable.

It would be desirable to develop new materials, such as intermediates,and new methods of using such newly developed materials, to make, forexample, indeno-fused naphthols and related materials. In addition, itwould be desirable that such newly developed materials and methodsprovide improvements, such as, higher yields, a reduced number ofsynthetic steps, and reduced costs relative to previous syntheticmethods.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a method offorming an indeno-fused ring compound, such as an A and B ring fusedinden-6-ol compound, represented by the following Formula I,

With reference to Formula I, Ring-A and Ring-B are each independentlyselected from unsubstituted aryl, substituted aryl, unsubstituted fusedring aryl, substituted fused ring aryl, unsubstituted heteroaryl, andsubstituted heteroaryl.

With further reference to Formula I, m and n are each independentlyselected from 0 to a value corresponding to as many positions on Ring-Aand Ring-B, respectively, to which an R¹ group or an R² group can bebonded. With some embodiments, m and n are each independently 0 to 4.Ring-A positions to which an R¹ group is not bonded, can instead havehydrogen groups bonded thereto. Similarly, Ring-B positions to which anR² group is not bonded, can instead have hydrogen groups bonded thereto.

In addition, R¹ for each m, and R² for each n, are in each caseindependently selected from: hydrocarbyl optionally interrupted with atleast one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, —N(R₁₁′)—where R₁₁′ is selected from hydrogen, hydrocarbyl or substitutedhydrocarbyl, —Si(OR₁₃′)_(k)(R₁₃′)_(j)—, where k and j are eachindependently selected from 0 to 2, provided that the sum of k and j is2, and each R₁₃′ is independently selected from hydrogen, hydrocarbyland substituted hydrocarbyl, and combinations of two or more thereof;substituted hydrocarbyl optionally interrupted with at least one of —O—,—S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, —N(R₁₁′)— where R₁₁′ isselected from hydrogen, hydrocarbyl or substituted hydrocarbyl,—Si(OR₁₃′)_(k)(R₁₃′)_(j)—, where k and j are each independently selectedfrom 0 to 2, provided that the sum of k and j is 2, and each R₁₃′ isindependently selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl, and combinations of two or more thereof; halogen; cyano;and —(R₁₁′)R₁₂′, wherein R₁₁′ and R₁₂′ are each independently selectedfrom hydrogen, hydrocarbyl or substituted hydrocarbyl, or R₁₁′ and R₁₂′together form a ring structure optionally including at least oneheteroatom.

The R³ and R⁴ groups of Formula I are each independently selected from:hydrogen; hydrocarbyl optionally interrupted with at least one of —O—,—S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, and —N(R₁₁′)— where R₁₁′ isselected from hydrogen, hydrocarbyl or substituted hydrocarbyl, andcombinations of two or more thereof; and substituted hydrocarbyloptionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—,—S(O)—, —SO₂—, —N═N—, and —N(R₁₁′)— where R₁₁′ is selected fromhydrogen, hydrocarbyl or substituted hydrocarbyl, and combinations oftwo or more thereof. With some embodiments, one or more of R¹, R², R³and R⁴ can in each case independently represent one or more precursorsof those groups as described above and further herein with reference to,for example, Formula I.

The R⁵ group of Formula I can be selected from hydrogen, —C(O)—R¹³ or—S(O)(O)R¹³, in which R¹³ is hydrocarbyl, or halohydrocarbyl.

The method of making the A and B ring fused inden-6-ol compoundrepresented by Formula I, comprises, reacting an unsaturated compoundsuch as a 2-(5-oxocyclopenta-1,3-dien-1-yl)acetic acid/ester compound,represented by the following Formula II, with (i) a reducing agentdefined as being selected from, but not limited to, an organo metalhydride, hydrogen, zinc and/or a mixture thereof. Alternatively, themethod of making the compound of Formula I comprises, reacting theunsaturated compound with (ii) a first nucleophile represented byFormula III (i.e., R⁴M¹). Reaction of either (i) or (ii) with theunsaturated compound results in the formation of a saturated compound,such as the A ring fused 2-(2-oxocyclopenta-3-en-1-yl)acetic acid/estercompound, represented by the following Formula IV,

With reference to Formulas II and IV, m, n, R¹, R², R³ and R⁴ are eachas described previously herein with reference to Formula I, or representprecursors of such groups. With reference to Formula III, R⁴ is anucleophile of R⁴ as described with regard to Formula I, and M¹ isselected from —Si(R¹⁸)₃, where each R¹⁸ is independently selected fromC₁-C₈ alkyl, or M¹ represents a counterion comprising a metal selectedfrom Mg, Li, Mn, Cu, Zn, and combinations thereof. With furtherreference to Formulas II and IV, R¹⁶ in each case is independentlyselected from hydrogen, hydrocarbyl and substituted hydrocarbyl.

The method of making the A and B ring fused inden-6-ol compoundrepresented by Formula I, further comprises, reacting the saturatedcompound represented by Formula IV with a second nucleophile representedby the following Formula V, thereby forming a substituted intermediaterepresented by at least one of the following Formulas VI, VII and VIII,

With reference to the second nucleophile represented by Formula V:Ring-B is a nucleophile of Ring-B as described with regard to Formula I;M2 represents a counterion comprising a metal selected from Mg, Li, Mn,Cu, Zn, Ln, and combinations thereof; and m and R² are each as describedpreviously herein with regard to Formula I, or R² represents a precursorof such groups as described with reference to Formula I. With referenceto the substituted intermediates represented by Formulas VI, VII andVIII, m, n, R¹, R², R³ and R⁴ are each as described previously hereinwith reference to Formula I, or represent precursors of such groups.

The method of making the A and B ring fused inden-6-ol compoundrepresented by Formula I, further comprises, converting the substitutedintermediate represented by at least one of Formulas VI, VII and VIII tothe compound represented by Formula I.

In accordance with the present invention, there is further provided amethod of making an A and B ring fused indenopyran compound representedby the following Formula XV,

With reference to Formula XV, Ring-A, Ring-B, m, n, R¹, R², R³ and R⁴are each as previously described herein, for example, with regard to theindeno-fused ring compound represented by Formula I. Alternatively, oneor more of R¹, R², R³ and R⁴ can in each case independently representone or more precursors of the those groups as described above andfurther herein with reference to, for example, Formula I.

The B and B′ groups of the compound represented by Formula XV are eachindependently selected from unsubstituted aryl, substituted aryl,unsubstituted heteroaryl, substituted heteroaryl, polyalkoxy, andpolyalkoxy having a polymerizable group. Alternatively B and B′, ofFormula X, taken together can form a ring structure selected fromunsubstituted fluoren-9-ylidene, substituted fluoren-9-ylidene,saturated spiro-monocyclic hydrocarbon ring, saturated spiro-bicyclichydrocarbon ring, and spiro-tricyclic hydrocarbon ring.

The method of forming the compound represented by Formula XV comprises,reacting an unsaturated compound represented by Formula II, with (i) areducing agent or (ii) a first nucleophile represented by Formula III,thereby forming a saturated compound represented by Formula IV, each asdescribed previously herein. The method further comprises, reacting thesaturated compound represented by Formula IV with a second nucleophilerepresented by Formula V, which results in the formation of asubstituted intermediate represented by at least one of Formulas VI, VIIand VIII, each as described previously herein. The substitutedintermediate represented by at least one of Formulas VI, VII and VIII,is next converted to an indeno-fused ring compound represented byFormula I, as described previously herein.

The method of forming the compound represented by Formula XV furthercomprises, reacting compound represented by Formula I with a propargylalcohol represented by the following Formula XVI, which results information of the compound represented by Formula XV,

The B and B′ groups of the propargyl alcohol represented by Formula XVI,are each as described previously herein with regard to the compoundrepresented by Formula XV. Alternatively, one or more of the B and B′groups of Formula XVI, can in each case independently represent one ormore precursors of the those groups as described above and furtherherein with reference to, for example, Formula XV.

There is further provided in accordance with the present invention, anunsaturated compound represented by Formula II, as described previouslyherein. The unsaturated compound represented by Formula II, can befurther described and referred to herein as an A-ring fused2-(5-oxocyclopenta-1,3-dien-1-yl)acetic acid/ester compound.

As used herein and in the claims, the term “actinic radiation” meanselectromagnetic radiation that is capable of transforming a photochromicmaterial from one form or state to another.

As used herein and in the claims, the term “photochromic” means havingan absorption spectrum for at least visible radiation that varies inresponse to absorption of at least actinic radiation. Further, as usedherein, the term “photochromic material” means any substance that isadapted to display photochromic properties, i.e., adapted to have anabsorption spectrum for at least visible radiation that varies inresponse to absorption of at least actinic radiation, and which includesat least one photochromic compound.

As used herein and in the claims, molecular weight values of polymers,such as weight average molecular weights (Mw) and number averagemolecular weights (Mn), are determined by gel permeation chromatographyusing appropriate standards, such as polystyrene standards.

As used herein and in the claims, polydispersity index (PDI) valuesrepresent a ratio of the weight average molecular weight (Mw) to thenumber average molecular weight (Mn) of the polymer (i.e., Mw/Mn).

As used herein and in the claims, the term “halo” and similar terms,such as halo group, halogen, and halogen group means F, CI, Br and/or I,such as fluoro, chloro, bromo and/or iodo.

Unless otherwise indicated, all ranges or ratios disclosed herein are tobe understood to encompass any and all subranges or subratios subsumedtherein. For example, a stated range or ratio of “1 to 10” should beconsidered to include any and all subranges between (and inclusive of)the minimum value of 1 and the maximum value of 10; that is, allsubranges or subratios beginning with a minimum value of 1 or more andending with a maximum value of 10 or less, such as but not limited to, 1to 6.1, 3.5 to 7.8, and 5.5 to 10.

As used herein and in the claims, the articles “a”, “an”, and “the”include plural referents unless otherwise expressly and unequivocallylimited to one referent.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be under stood asmodified in all instances by the term “about.”

DETAILED DESCRIPTION OF THE INVENTION

Various groups of the compounds and intermediates described previouslyand further herein, such as but not limited to the R¹, R², R³ and R⁴groups of the A and B ring fused inden-6-ol compounds represented byFormula I, can in each case be independently selected from hydrocarbyland substituted hydrocarbyl.

As used herein and in the claims the term “hydrocarbyl” and similarterms, such as “hydrocarbyl substituent” and “hydrocarbyl group” means:linear or branched C₁-C₂₀ alkyl (e.g., linear or branched C₁-C₁₀ alkyl);linear or branched C₂-C₂₀ alkenyl (e.g., linear or branched C₂-C₁₀alkenyl); linear or branched C₂-C₂₀ alkynyl (e.g., linear or branchedC₂-C₁₀ alkynyl); C₃-C₁₂ cycloalkyl (e.g., C₃-C₁₀ cycloalkyl); C₃-C₁₂heterocycloalkyl (having at least one hetero atom in the cyclic ring);C₅-C₁₈ aryl (including polycyclic aryl groups) (e.g., C₅-C₁₀ aryl);C₅-C₁₈ heteroaryl (having at least one hetero atom in the aromaticring); and C₆-C₂₄ aralkyl (e.g., C₆-C₁₀ aralkyl).

Representative alkyl groups include but are not limited to methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representativealkenyl groups include but are not limited to vinyl, allyl and propenyl.Representative alkynyl groups include but are not limited to ethynyl,1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representativecycloalkyl groups include but are not limited to cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl substituents.Representative heterocycloalkyl groups include but are not limited totetrahydrofuranyl, tetrahydropyranyl and piperidinyl. Representativearyl groups include but are not limited to phenyl and naphthyl.Representative heteroaryl groups include but are not limited to furanyl,pyranyl and pyridinyl. Representative aralkyl groups include but are notlimited to benzyl, and phenethyl.

The term “substituted hydrocarbyl” as used herein and in the claimsmeans a hydrocarbyl group in which at least one hydrogen thereof hasbeen substituted with a group that is other than hydrogen, such as, butnot limited to, halo groups, hydroxyl groups, ether groups, thiolgroups, thio ether groups, carboxylic acid groups, carboxylic acid estergroups, phosphoric acid groups, phosphoric acid ester groups, sulfonicacid groups, sulfonic acid ester groups, nitro groups, cyano groups,hydrocarbyl groups (e.g., alkyl, alkenyl, alkynyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl, and aralkyl groups), and aminegroups, such as —N(R₁₁′)(R₁₂′) where R₁₁′ and R₁₂′ are eachindependently selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl, or R₁₁′ and R₁₂′ together form a cyclic ring optionallyincluding at least one heteroatom (e.g., —O— and/or —S—).

The term “substituted hydrocarbyl” is inclusive of halohydrocarbyl (orhalo substituted hydrocarbyl) substituents. The term “halohydrocarbyl”as used herein and in the claims, and similar terms, such as halosubstituted hydrocarbyl, means that at least one hydrogen atom of thehydrocarbyl (e.g., of the alkyl, alkenyl, alkynyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl, and aralkyl groups) is replaced witha halogen atom selected from chlorine, bromine, fluorine and iodine. Thedegree of halogenation can range from at least one hydrogen atom beingreplaced by a halogen atom (e.g., a fluoromethyl group) to fullhalogenation (perhalogenation) in which all replaceable hydrogen atomson the hydrocarbyl group have been replaced by a halogen atom (e.g.,trifluoromethyl or perfluoromethyl). Correspondingly, the term“perhalohydrocarbyl group” as used herein and in the claims means ahydrocarbyl group in which all replaceable hydrogens have been replacedwith a halogen. Examples of perhalohydrocarbyl groups include, but arenot limited to, perhalogenated phenyl groups and perhalogenated alkylgroups.

The hydrocarbyl and substituted hydrocarbyl groups from which variousgroups and substituents, such as R¹, R², R³ and R⁴, can each beselected, can in each case be independently and optionally interruptedwith at least one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—,and —N(R₁₁′)—. As used herein and in the claims, by interrupted with atleast one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, and—N(R₁₁′)—, means that at least one carbon of, but less than all of thecarbons of, the hydrocarbyl group or substituted hydrocarbyl group, isin each case independently replaced with one of the recited divalentlinking groups. The hydrocarbyl and substituted hydrocarbyl groups canbe interrupted with two or more of the above recited linking groups,which can be adjacent each other or separated by one or more carbons.

As used herein and in the claims, recitations of “linear or branched” or“linear, branched or cyclic” groups, such as linear or branched alkyl,or linear, branched or cyclic alkyl, are herein understood to include: amethylene group or a methyl group; groups that are linear, such aslinear C₂-C₂₅ alkyl groups; groups that are appropriately branched, suchas branched C₃-C₂₅ alkyl groups; and groups that are appropriatelycyclic, such as C₃-C₂₅ cycloalkyl (or cyclic C₃-C₂₅ alkyl) groups.

As used herein and in the claims, the term “precursor” and relatedterms, such as “precursors” with regard to the various groups, forexample, R¹, R², R³, R⁴, B and B′, of the compounds and intermediatesdescribed herein, for example, the indeno-fused ring compoundsrepresented by Formula I, the indeno-fused ring pyran compoundsrepresented by Formula XV, and the unsaturated compounds represented byFormula II, means a group that can be converted in one or more steps tothe final or desired group. For purposes of non-limiting illustration: aprecursor of a hydroxyl group (—OH) includes, but is not limited to, acarboxylic acid ester group (—OC(O)R where R is hydrogen or anoptionally substituted hydrocarbyl); and a precursor of a carboxylicacid ester group (—OC(O)R) includes, but is not limited to, a hydroxylgroup (—OH), which can be reacted, for example, with a carboxylic acidhalide, such as acetic acid chloride (or acetyl chloride).

As used herein and in the claims, unless otherwise indicated,left-to-right representations of linking groups, such as divalentlinking groups, are inclusive of other appropriate orientations, suchas, right-to-left orientations. For purposes of non-limitingillustration, the left-to-right representation of the divalent linkinggroup —C(O)O—, is inclusive of the right-to-left representation thereof,—O(O)C—.

The unsaturated compound represented by Formula II of the presentinvention, and which can be used in the methods of the presentinvention, can be prepared by appropriate methods. With some embodimentsof the present invention, the unsaturated compound represented byFormula II can be prepared by a reaction between a Ring-A R³ ketone anda succinic acid diester, as represented by the following Scheme-1.

With reference to Scheme-1, the Ring-A R³ ketone (a) is reacted with asuccinic acid diester (b), in which each R¹⁹ is an optionallysubstituted hydrocarbyl groups, such as an alkyl group (e.g., each R¹⁹can be ethyl), in the presence of a strong base, such as an alkali metalalkoxide, such as NaOR¹⁹ (e.g., sodium ethoxide), or KOR¹⁹ (e.g.,potassium t-butoxide) The reaction of Scheme-1 is conducted underappropriate conditions, such as at a temperature of from 0° C. to 110°C., under an inert atmosphere, and in the presence of an appropriatesolvent, such as toluene. The resulting intermediate material (notshown) is washed with one or more protonic acids, such as dilute aqueoushydrochloric acid. This workup of the reaction is described in furtherdetail in the Examples. The reaction represented by Scheme-1 results inthe formation of acid-ester intermediates represented by Formulas (c-1)and (c-2). The acid-ester intermediates can be converted into di-acidsin aqueous base.

The di-acid or acid-ester intermediates represented by Formulas (c-1)and (c-2) of Scheme-1, can be converted to succinic anhydrideintermediates, as represented by the following Scheme-2.

With reference to Scheme-2, the intermediates represented by Formulas(c-1) and (c-2) are converted to the succinic anhydride intermediatesrepresented by Formulas (d-1) and (d-2) in the presence of a protonicacid, such as dodecyclbezene sulfonic acid (DDBSA), with concurrentremoval of alcohol (R¹⁹OH) or water when R¹⁹ is hydrogen. The conversionrepresented by Scheme-2 is typically conducted under conditions ofelevated temperature, such as at the refluxing temperature of thesolvent in the presence of a suitable solvent, such as toluene, with theuse of a Dean-Stark trap for water removal. Acid chloride can also beused to make the anhydride.

The succinic anhydride intermediates represented by Formulas (d-1) and(d-2) can next be converted to the unsaturated compound represented byFormula II-2 and II, as represented by the following Scheme-3.

With reference to Scheme-3, the conversion of the succinic anhydrideintermediates represented by Formulas (d-1) and (d-2) to the unsaturatedcompounds represented by Formulas II-2 and II, can be conducted in thepresence of a Lewis acid. Examples of Lewis acids include, but are notlimited to, aluminum halide, such as aluminum chloride (AlCl₃), titaniumtetrachloride (TiCl₄), tin tetrachloride (SnCl₄), boron trifluoride(BF₃), and combinations or mixtures thereof. The conversion representedby Scheme-3 is typically conducted in the presence of a suitablesolvent, such as methylene chloride , and under appropriate conditions,such as a temperature of from 0° C. to 60° C., and an inert atmosphere(e.g., with a nitrogen sweep). The obtained acid represented by FormulaII-a can be used as is for the next reaction or be converted to theester represented by Formula II and then used.

With some embodiments of the present invention, the method of formingthe indeno-fused ring compound represented by Formula I can involveinitially reacting the unsaturated compound represented by Formula IIwith a reducing agent or a first nucleophile represented by Formula III(i.e., R⁴M¹ as described previously herein), so as to form the saturatedcompound or intermediate represented by Formula IV, as represented bythe following Scheme-4.

With the reaction represented by Scheme-4, the unsaturated compoundrepresented by Formula II is typically reacted with either a reducingagent or a nucleophile represented by Formula III. The reactionrepresented by Scheme-4 can be referred to as a 1,4-addition reaction orstep. When a reducing agent is used, R⁴ of the saturated compoundrepresented by Formula IV is typically hydrogen. The metal hydridereducing agent can, in some embodiments, be selected from sodiumborohydride and lithium aluminum hydride, or an organo metal hydridereducing agent. The organo metal hydride reducing agent can be one ormore di(C₁-C₂₀ alkyl) aluminum hydride reducing agents, such as one ormore di(C₁-C₆ alkyl) aluminum hydride reducing agents, e.g., diethylaluminum hydride and diisobutyl aluminum hydride.

With further reference to the reaction represented by Scheme-4, thereducing agent and the nucleophile represented by Formula III aretypically present in at least an equimolar or greater amount relative tothe amount of unsaturated compound represented by Formula II. Accordingto some embodiments of the present inven^(t)ion, M¹ of Formula III alsoincludes a halogen, and can be represented by (M¹X)⁺, in which X is ahalogen. M¹ of Formula III can be selected from (MgX)⁺, in which X isselected from halogen, such as Cl (e.g., (MgCl)⁺).

With some embodiments of the present invention, the nucleophilerepresented by Formula III is a Grignard reagent, and the reactionrepresented by Scheme-4 is a Grignard reaction, which is conducted underGrignard reaction conditions. Copper (I) halide and manganese chloridetypically are added into the Gregnard reaction to facilitate the1,4-addition reaction as discussed in Chem. Rev. 2009, 109, pp.1434-1476. The reaction represented by Scheme-4 is typically conductedin the presence of an appropriate solvent, such as tetrahydrofuran(THF), and under conditions of ambient pressure (e.g., approximately ¹atm), under an inert atmosphere (e.g., under a nitrogen sweep).Themethod of forming the indeno-fused ring compound represented by FormulaI, with some embodiments of the present invention, typically nextinvolves reacting the saturated compound represented by Formula IV witha second nucleophile represented by Formula V, so as to result in theformation of at least one substituted intermediate (e.g., Ring-Bsubstituted intermediate) represented by at least one of Formulas VI,VII and VIII, as represented by the following Scheme-5.

As discussed previously herein, the second nucleophile represented byFormula V, represents a counterion, and in particular a cation, thatincludes a metal selected from Mg, Li, Mn, Cu, Zn, Ln and combinationsof two or more thereof. Typically, the counterion M² also includes ahalogen, and can be represented by (M²X)⁺. With some embodiments of thepresent invention, the counterion M² includes Mg and a halogen, such asCl (e.g., (MgCl)⁺).

With some embodiments of the present invention, the second nucleophilerepresented by Formula V is a Grignard reagent, and the reactionrepresented by Scheme-5 is a Grignard reaction, which is conducted underGrignard reaction conditions. The reaction represented by Scheme-5 istypically conducted in the presence of an appropriate solvent, such astetrahydrofuran (THF), and under conditions of ambient pressure (e.g.,approximately 1 atm), under an inert atmosphere (e.g., under a nitrogensweep), elevated temperature, such as from −20° C. to 65° C., or from−10° C. to 50° C., or from 0° C. to 40° C., and optionally at therefluxing temperature of the solvent.

With further reference to the reaction represented by Scheme-5, thecarboxylic acid group of the saturated compound represented by FormulaIV typically deactivates a molar equivalent of the second nucleophilerepresented by Formula V. To address this deactivation, additionalsecond nucleophile represented by Formula V can be added to the reactionvessel. With some embodiments, for every mole of saturated compoundrepresented by Formula IV, two or more moles of second nucleophilerepresented by Formula V are added to or present within the reactionvessel. With further embodiments of the present invention, when R¹⁶ ishydrogen, the carboxylic acid group of the saturated compoundrepresented by Formula IV can be protected, for example converted to anoxazoline group, as will be discussed in further detail herein.

When more than one substituted intermediate represented by FormulasVI-2, VII-2 and VIII is formed, for example as represented in Scheme-5,the mixture of such intermediates can optionally be separated andisolated from each other before the next step of the synthesis.Art-recognized separation and isolation methods can be used, such aschromatography . Typically, when more than one substituted intermediaterepresented by Formulas VI-2, VII-2 and VIII is formed, the mixture ofsuch intermediates is not separated or isolated from each other, and isused as a mixture of intermediates in the next step of the synthesis.

The substituted intermediate represented by at least one of FormulasVI-2, VII-2 and VIII is converted to the compound represented by FormulaI, in the next step of the method of the present invention. Thisconversion can be conducted in substantially one step in the presence ofa protonic acid or acid anhydrides and acid chlorides as represented bythe following Scheme-6.

When conducted in the presence of a protonic acid, the conversion asrepresented by Scheme-6 results in the formation of the compoundrepresented by Formula I, in which R⁵ is hydrogen. Theconversion/reaction represented by Scheme-6 is typically conducted underelevated temperature, for example at a temperature from 110° C. to 140°C., or from 120° C. to 135° C., or from 125° C. to 130° C., underconditions of ambient pressure (e.g., approximately 1 atm), and under aninert atmosphere, such as a nitrogen sweep. Examples of protonic acidsthat can be used in the conversion represented by Scheme-6 include, butare not limited to, carboxylic acids (e.g., acetic, proponoic, and/orbutanoic acid), sulfonic acids (e.g., R—S(O)(O)—OH, where R is selectedfrom hydrocarbyl or substituted hydrocarbyl, such asperhalohydrocarbyl), phosphoric acids (e.g., orthophosphoric acid and/orrelated combinations thereof), and combinations thereof. The protonicacid can be present in an amount ranging from 0.1 molar percent to 2,000molar percent, i.e., from a catalytic amount to an excess amount, basedon 100 molar percent of the starting materials. An excess amount wouldoccur if the protonic acid was used as part of the solvent, e.g.phosphoric acid.

When conducted in the presence of acid anhydride, conversion of thesubstituted intermediate represented by at least one of Formulas VI-2,VII-2 and VIII to the compound represented by Formula I, is conducted intwo steps. Initially an ester intermediate represented by Formula IX isformed, which is then reacted with a protonic acid so as to form thecompound represented by Formula I, as represented by the followingScheme-7.

With reference to Scheme-7, the R¹⁴ group of the ester intermediaterepresented by Formula IX is selected from —C(O)—R¹³ and —S(O)(O)R¹³,where R¹³ in each case is independently selected from hydrocarbyl (e.g.,C₁-C₁₀ alkyl) and halohydrocarbyl (e.g., C₁-C₁₀ perhaloalkyl).

The initial conversion or reaction of step-(a) of Scheme-7, is typicallyconducted in the presence of a material selected from carboxylic acidhalide, carboxylic acid anhydride, sulfonyl halide, sulfonyl anhydrideand combinations thereof. The carboxylic acid halide, carboxylic acidanhydride, sulfonyl halide and/or sulfonyl anhydride is typicallypresent in at least an equimolar amount relative to the substitutedintermediate represented by at least one of Formulas VI, VII and VIII.Carboxylic acid halides that can be used in step-(a), can be representedby the structure, R^(c)—C(O)—X, where R^(c) is selected from hydrocarbylor substituted hydrocarbyl, and X is selected from halogen (e.g., Cl).Sulfonyl halides that can be used in step-(a), can be represented by theformula, R^(d)—S(O)(O)—X, where R^(d) is selected from hydrocarbyl orsubstituted hydrocarbyl, and X is selected from halogen (e.g., Cl).Carboxylic acid anhydrides that can be used in step-(a), can berepresented by the formula, R^(e)—C(O)—O—C(O)—R^(f), where R^(e) andR^(f) are each independently selected from hydrogen, hydrocarbyl, andsubstituted hydrocarbyl (e.g., halohydrocarbyl, such as C₁-C₁₀perhaloalkyl, e.g., —CF₃). Sulfonyl anhydrides that can be used instep-(a), can be represented by the formulas R^(e)—S(O₂)—O—S(O₂)—R^(h),where R^(g) and R^(h) are each independently selected from hydrocarbylor substituted hydrocarbyl.

The ester intermediate represented by Formula IX is converted to thecompound represented by Formula I (in which R⁵ is hydrogen) in step-(b)of Scheme-7 by hydrolysis in the presence of a protonic acid or base.The protonic acid can be selected from hydrogen halides (HX, where X ishalogen) such as HCl, sulfonic acids, phosphoric acids, and/orcarboxylic acids. Examples of sulfonic acids include, but are notlimited to p-toluenesulfonic acid. Examples of phosphoric acids include,but are not limited to phosphoric acid. Examples of carboxylic acidsinclude, but are not limited to trifluoroacetic acid. The base can beselected from sodium hydroxide, potassium hydroxide and potassiumcarbonate.

The protonic acid or base is typically present in an excess amountrelative to the amount of ester intermediate represented by Formula IX.For example the conversion of step-(b) of Scheme-7 can be conducted inthe presence of concentrated hydrogen halide acid, such as concentratedHCl, or a base, such as potassium carbonate . The conversion of step-(b)is typically conducted in the presence of a solvent (e.g., methanol),under reflux conditions, for example at a temperature from 65° C. to150° C., or from 80° C. to 140° C., or from 100° C. to 130° C., underconditions of ambient pressure (e.g., approximately 1 atm), and under aninert atmosphere, such as a nitrogen sweep.

The method of the present invention can result in the formation ofindeno-fused ring compounds represented by Formula I in a wide range ofyields. For example the method of the present invention can result inthe formation of indeno-fused ring compound represented by Formula I inyields of from 1 to 85 mole percent, based on theoretical moles ofindeno-fused ring compound that could be produced. Typically, the methodof the present invention results in the formation of indeno-fused ringcompounds in yields of at least 5 mole percent, such as from 20 to 85mole percent, or from 30 to 75 mole percent, based on theoretical molesof indeno-fused ring compound that could be produced.

With some embodiments of the present invention, the carboxylic acidgroup represented by Formula II and IV, can be protected so as tominimize or prevent reaction between the protected carboxylic acid groupand the reducing agent or the first nucleophile represented by FormulaIII. Protection of the carboxylic acid group can also serve to minimizereaction between the carboxylic acid group of the saturated compoundrepresented by Formula IV (when R¹⁶ is hydrogen) and the secondnucleophile represented by Formula V. With some embodiments, thesaturated compound represented by Formula IV is converted to anoxazoline protected unsaturated compound represented by the followingFormula IIa,

With reference to the oxazoline protected unsaturated compoundrepresented by Formula IIa, m, R¹, R³ and Ring-A are each as describedpreviously herein with regard the unsaturated compound represented byFormula II. Alternatively, R¹ and R³ in each case independentlyrepresent one or more precursors of the those groups as described aboveand further herein with reference to, for example Formula II. Withfurther reference to the oxazoline protected unsaturated compoundrepresented by Formula IIa, R²⁰ and R²¹ are each independently selectedfrom hydrogen, hydrocarbyl, and substituted hydrocarbyl.

The oxazoline protected unsaturated compound represented by Formula IIacan be formed by suitable methods. With some embodiments, the oxazolineprotected unsaturated compound represented by Formula IIa can be formedby reaction of the unsaturated compound represented by Formula II (whenR¹⁶ is hydrogen) with an amino alcohol, such as2-amino-2-methyl-3-hydroxy propane, as represented by the followingScheme-8.

The reaction depicted in Scheme-8 is typically conducted in the presenceof a suitable solvent, such as xylene, and under appropriate refluxconditions.

The oxazoline protected unsaturated compound represented by Formula IIacan alternatively be formed by a multi-step synthetic scheme thatinvolves the formation of a carboxylic acid halide intermediate, asrepresented by the following Scheme-9.

In step-(a) of Scheme-9, thionyl chloride (SOCl₂) is reacted with theunsaturated compound represented by Formula II (where R¹⁶ is hydrogen)under art-recognized conditions, which results in formation of anunsaturated acid chloride intermediate represented by Formula II-1. Theunsaturated acid chloride intermediate represented by Formula II-1 isthen reacted in step-(b) with an amino alcohol, such as2-amino-2-methyl-3-hydroxy propane, which results in the formation ofthe unsaturated hydroxyl functional amide intermediate represented byFormula II-3. In step-(c), the unsaturated hydroxyl functional amideintermediate represented by Formula II-3 is cyclized to form theoxazoline protected unsaturated compound represented by Formula IIa inthe presence of thionyl chloride and base, such as sodium hydroxide.

The oxazoline protected unsaturated compound represented by Formula IIais next reacted with a reducing agent or a first nucleophile representedby Formula III (each as described previously herein), so as to form anoxazoline protected saturated compound represented by Formula IVa.

The reaction of the oxazoline protected unsaturated compound representedby Formula IIa with a reducing agent or a first nucleophile representedby Formula III, so as to form the oxazoline protected saturated compoundrepresented by Formula IVa, can be conducted in accordance with thedescription provided previously herein with regard to Scheme-4.Typically, however, an excess of organo metal hydride or firstnucleophile represented by Formula III, is not required. With someembodiments, a substantially equimolar amount of reducing agent or firstnucleophile represented by Formula III is reacted with the oxazolineprotected unsaturated compound represented by Formula IIa.

The oxazoline protected saturated compound represented by Formula IVa isthen reacted with the second nucleophile represented by Formula V,thereby forming an oxazoline protected substituted intermediate (e.g.,an oxazoline protected Ring-B substituted intermediate) represented byat least one of Formula VIa and Formula VIIa,

The reaction of oxazoline protected saturated compound represented byFormula IVa with the second nucleophile represented by Formula V, so asto form the oxazoline protected substituted intermediate represented byFormulas VIa and/or VIIa, can be conducted in accordance with thedescription provided previously herein with regard to Scheme-5.Typically, however, an excess of second nucleophile represented byFormula V, is not required. With some embodiments, a substantiallyequimolar or greater amount of second nucleophile represented by FormulaV is reacted with the oxazoline protected saturated compound representedby Formula IVa.

The oxazoline protected substituted intermediate represented by FormulasVIa and/or VIIb is then converted to the substituted intermediate (e.g.,Ring-B substituted intermediate) represented by at least one of FormulasVI-2, VII-2 and VIII. More particularly, the oxazoline group is removedfrom the oxazoline protected substituted intermediate represented byFormulas VIa and/or VIIb, thus resulting in formation of the substitutedintermediate represented by at least one of Formulas VI-2, VII-2 andVIII, as represented by the following Scheme-10.

With reference to Scheme-10, removal of the oxazoline group is typicallyconducted in the presence of a protonic acid, and in particular aninorganic acid, such as concentrated HCl, and under appropriate refluxconditions. Appropriate work-up of the resulting substitutedintermediate represented by at least one of Formulas VI-2, VII-2 andVIII is typically conducted, for example to remove the amino alcoholand/or salt thereof.

The compounds prepared by the method of the present invention can beused in numerous applications, such as additives in compositions, or asintermediates in the synthesis of additional compounds, such asnon-photochromic (or static) dyes and photochromic dyes. Embodiments ofthe present invention also include a method of making an A and B ringfused indenopyran compound represented by Formula XV, which involvesforming the compound represented by Formula I, as described previouslyherein, and then reacting the compound represented by Formula I with apropargyl alcohol represented by Formula XVI. Reaction of the compoundrepresented by Formula I and the propargyl alcohol represented byFormula XVI can be represented by the following Scheme-11.

With reference to Scheme-11, when R⁵ is hydrogen the compoundrepresented by Formula I is reacted or coupled with the propargylalcohol represented by Formula XVI in the presence of a catalytic amountof a protonic acid, such as dodecyl benzene sulfonic acid (DDBSA) orpara-toluene sulfonic acid (pTSA), in a suitable solvent, such as ahaloalkyl (e.g., trichloromethane), under an inert atmosphere (e.g., anitrogen sweep), and at an temperature range, for example, from 25° C.to 110° C., or from 35° C. to 100° C., or from 50° C. to 80° C.

With further reference to Scheme-11, when R⁵ is —C(O)—R¹³ or—S(O)(O)R¹³, the reaction can include an initial step (not shown) thatinvolves the removal of the R⁵ group, which typically involves reflux inthe presence of a protonic acid, such as hydrochloric acid. The productafter hydrolysis is isolated from the reaction mixture before reactionwith the propargyl compound.

The groups and substituents of the compounds described previously andfurther herein, such as the A and B ring fused inden-6-ol compounds(e.g., represented by Formula I), the unsaturated compounds representedby Formula II, the A and B ring fused indenopyran compounds (e.g.,represented by Formula XV), and the compounds and intermediates used intheir preparation, are described in further detail as follows.

The Ring-A and Ring-B groups of the compounds described herein, such asthose compounds represented by Formulas I, II and XV, can in each casebe independently selected from unsubstituted aryl, substituted aryl,unsubstituted fused ring aryl, substituted fused ring aryl,unsubstituted heteroaryl, and substituted heteroaryl. The substituentsof the substituted aryl, fused ring aryl and heteroaryl groups can eachbe independently selected from hydrocarbyl groups and substitutedhydrocarbyl groups, which each can be optionally interrupted with atleast one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, and—N(R₁₁′)—, as described previously herein. Examples of aryl groups fromwhich Ring-A and Ring-B can each be independently selected include, butare not limited to, phenyl and biphenyl. Examples of fused ring arylgroups from which Ring-A and Ring-B can each be independently selectedinclude, but are not limited to, polycyclic aromatic hydrocarbons, suchas naphthyl and anthracenyl. Examples of heteroaryl groups from whichRing-A and Ring-B can each be independently selected include, but arenot limited to, furanyl, pyranyl and pyridinyl.

With some embodiments of the present invention, R¹ for each m, and R²for each n, are in each case independently selected from: a reactivesubstituent; a compatiblizing substituent; halogen selected from fluoroand chloro; C₁-C₂₀ alkyl; C₃-C₁₀ cycloalkyl; substituted orunsubstituted phenyl; or —O—R₁₀′ or —C(O)—R₁₀′ or —C(O)—OR₁₀′, whereinR₁₀′ is hydrogen, C₁-C₂₀ alkyl, phenyl(C₁-C₂₀)alkyl, mono(C₁-C₂₀)alkylsubstituted phenyl(C₁-C₂₀)alkyl, mono(C₁-C₂₀)alkoxy substitutedphenyl(C₁-C₂₀)alkyl, (C₁-C₂₀)alkoxy(C₂-C₂₀)alkyl, C₃-C₁₀ cycloalkyl, ormono(C₁-C₂₀)alkyl substituted C₃-C₁₀ cycloalkyl. The phenyl substituents(i.e., the substituents of the substituted phenyl) can be selected fromhydroxyl, halogen, carbonyl, C₁-C₂₀ alkoxycarbonyl, cyano,halo(C₁-C₂₀)alkyl, C₁-C₂₀ alkyl or C₁-C₂₀ alkoxy.

With some further embodiments, R¹ for each m, and R² for each n, are ineach case independently and more particularly selected from: C₁-C₆alkyl; C₃-C₇ cycloalkyl; substituted or unsubstituted phenyl; —OR₁₀′ or—OC(═O)R₁₀′, wherein R₁₀′ is hydrogen, C₁-C₆ alkyl, phenyl(C₁-C₃)alkyl,mono(C₁-C₆)alkyl substituted phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxysubstituted phenyl(C₁-C₃)alkyl, (C₁-C₆)alkoxy(C₂-C₄)alkyl, C₃-C₇cycloalkyl, or mono(C₁-C₄)alkyl substituted C₃-C₇ cycloalkyl. The phenylsubstituents (i.e., the substituents of the substituted phenyl) can bemore particularly selected from hydroxyl, halogen, carbonyl, C₁-C₆alkoxycarbonyl, cyano, halo(C₁-C₆)alkyl, C₁-C₆ alkyl or C₁-C₆ alkoxy.

Alternatively or in addition to the previously recited classes andexamples, R¹ for each m, and R² for each n, can in each case beindependently selected from, —N(R₁₁′)R₁₂′, wherein R₁₁′ and R₁₂′ areeach independently hydrogen, C₁-C₂₀ alkyl, phenyl, naphthyl, furanyl,benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl,fluorenyl, C₁-C₂₀ alkylaryl, C₃-C₁₀ cycloalkyl, C₄-C₂₀ bicycloalkyl,C₅-C₂₀ tricycloalkyl or C₁-C₂₀ alkoxyalkyl, wherein said aryl group isphenyl or naphthyl, or R₁₁′ and R₁₂′ come together with the nitrogenatom to form a C₃-C₂₀ hetero-bicycloalkyl ring or a C₄-C₂₀hetero-tricycloalkyl ring.

Further alternatively or in addition to the previously recited classesand examples, R¹ for each m, and R² for each n, can in each case beindependently selected from, a nitrogen containing ring represented bythe following graphic Formula XIIA,

With the nitrogen ring substituent represented by general Formula XIIA,each —Y— is independently chosen for each occurrence from —CH₂₋,—CH(R₁₃′)—, —C(R₁₃′)₂—, —CH(aryl)-, —C(aryl)₂-, and —C(R₁₃′)(aryl)-, andZ is —Y—, —O—, —S—, —S(O)—, —SO₂—, —NH—, —N(R₁₃′), or —N(aryl)-, whereineach R₁₃′ is independently C₁-C₂₀ alkyl (e.g., C₁-C₆ alkyl), each arylis independently phenyl or naphthyl, m is an integer 1, 2 or 3, and p isan integer 0, 1, 2, or 3 and provided that when p is 0, Z is —Y—.

Additionally or alternatively, R¹ for each m, and R² for each n, can ineach case also be independently selected from a nitrogen containing ringsubstituent represented by general formula XIIB and/or general formulaXIIC:

For the nitrogen containing ring substituents represented by generalformulas XIIB and XIIC, R₁₅, R₁₆, and R₁₇ are each independentlyhydrogen, C₁-C₂₀ alkyl (e.g., C₁-C₆ alkyl), phenyl, or naphthyl, or thegroups R₁₅ and R₁₆ together form a ring of 5 to 8 carbon atoms and eachR^(d) is independently for each occurrence selected from C₁-C₂₀ alkyl(e.g., C₁-C₆ alkyl), C₁-C₂₀ alkoxy (e.g., C₁-C₆ alkoxy), fluoro orchloro, and Q is an integer 0, 1, 2, or 3.

Further alternatively or additionally, R¹ for each m, and R² for each n,can in each case also be independently selected from, unsubstituted,mono-, or di-substituted C₄-C₁₈ spirobicyclic amine, or unsubstituted,mono-, and di-substituted C₄-C₁₈ spirotricyclic amine, wherein thesubstituents are independently aryl, C₁-C₂₀ alkyl (e.g., C₁-C₆ alkyl),C₁-C₂₀ alkoxy (e.g., C₁-C₆ alkoxy), or phenyl(C₁-C₂₀)alkyl (e.g.,phenyl(C₁-C₆)alkyl).

With some embodiments of the present invention, two adjacent R¹ groups,and/or two adjacent R² groups, can together form a group represented bythe following general formula XIID or general formula XIIE,

With the groups represented by general formulas XIID and XIIE, T and T′are each independently oxygen or the group —NR₁₁—, where R₁₁, R₁₅, andR₁₆ are each as set forth and described previously herein.

The R³ and R⁴ groups, with some embodiments of the present invention,can each be independently selected from: a reactive substituent; acompatiblizing substituent; hydrogen; hydroxy; C₁-C₂₀ alkyl (e.g., C₁-C₆alkyl); C₁-C₂₀ haloalkyl (e.g., C₁-C₆ haloalkyl); C₃-C₁₀ cycloalkyl(e.g., C₃-C₇ cycloalkyl); allyl; benzyl; or mono-substituted benzyl. Thebenzyl substituents can be chosen from halogen, C₁-C₂₀ alkyl (e.g.,C₁-C₆ alkyl) or C₁-C₂₀ alkoxy (e.g., C₁-C₆ alkoxy).

The R³ and R⁴ groups with some further embodiments of the presentinvention, can each be independently selected from, an unsubstituted,mono- di-or tri-substituted group chosen from phenyl, naphthyl,phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl,benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, or indolyl.The group substituents can in each case be independently chosen fromhalogen, C₁-C₂₀ alkyl (e.g., C₁-C₆ alkyl) or C₁-C₂₀ alkoxy (e.g., C₁-C₆alkoxy).

The R³ and R⁴ groups can also, with some embodiments of the presentinvention, each be independently selected from a mono-substitutedphenyl, in which the phenyl has a substituent located at the paraposition thereof, which is a linking group, —(CH₂)_(t)— or—O—(CH₂)_(t)—, that is connected to an aryl group which is a member of a(or another) photochromic material, such as a naphthopyran, anindeno-fused naphthopyran, or benzopyran, and t is chosen from theinteger 1, 2, 3, 4, 5 or 6.

Alternatively, the R³ and R⁴ groups can each be independently selectedfrom the group —CH(R¹⁰)G, in which R¹⁰ is hydrogen, C₁-C₂₀ alkyl (e.g.,C₁-C₆ alkyl) or the unsubstituted, mono- or di-substituted aryl groupsphenyl or naphthyl, and G is —CH₂OR¹¹, in which R¹¹ is hydrogen,—C(O)R¹⁰, C₁-C₂₀ alkyl (e.g., C₁-C₆ alkyl), C₁-C₂₀ alkoxy(C₁-C₂₀)alkyl(e.g., C₁-C₃ alkoxy(C₁-C₆)alkyl), phenyl(C₁-C₂₀)alkyl (e.g.,phenyl(C₁-C₃)alkyl), mono(C₁-C₂₀)alkoxy substituted phenyl(C₁-C₂₀)alkyl(e.g., mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl), or theunsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl.The substituents of the phenyl and naphthyl groups can each beindependently selected from C₁-C₂₀ alkyl (e.g., C₁-C₆ alkyl) or C₁-C₂₀alkoxy (e.g., C₁-C₆ alkoxy).

With some embodiments of the present invention, R¹ for each m, and R²for each n, are in each case independently selected from unsubstitutedphenyl, substituted phenyl, C₁-C₆ alkyl, C₃-C₇ cycloalkyl, C₁-C₈haloalkyl, fluoro, chloro, and —O—R₁₀′. With further embodiments of thepresent invention, R³ and R⁴ are each independently selected fromhydrogen, C₁-C₈ alkyl, C₁-C₈ haloalkyl, and C₃-C₇ cycloalkyl.

In accordance with some further embodiments of the present invention, R¹for each m, and R² for each n, can in each case be independentlyselected from a group represented by the following Formula XIII,

—(S₁)_(c)-(Q₁-(S₂)_(d))_(d′)-(Q₂-(S₃)_(e))_(e′)-(Q₃-(S₄)_(f))_(f′)—S₅—P

With reference to Formula XIII, Q₁, Q₂, and Q₃ are each independentlychosen from, a divalent group chosen from, an unsubstituted or asubstituted aromatic group, an unsubstituted or a substituted alicyclicgroup, an unsubstituted or a substituted heterocyclic group, andmixtures thereof.

The substituents of the substituted aromatic groups, substitutedalicyclic groups and substituted heterocyclic groups from which each ofQ₁, Q₂, and Q₃ can be selected, are independently chosen from: a grouprepresented by P (as will be described in further detail herein); liquidcrystal mesogens; halogen; poly(C₁-C₁₈ alkoxy); C₁-C₁₈ alkoxycarbonyl;C₁-C₁₈ alkylcarbonyl; C₁-C₁₈ alkoxycarbonyloxy; aryloxycarbonyloxy;perfluoro(C₁-C₁₈)alkoxy; perfluoro(C₁-C₁₈)alkoxycarbonyl;perfluoro(C₁-C₁₈)alkylcarbonyl; perfluoro(C₁-C₁₈)alkylamino;di-(perfluoro(C₁-C₁₈)alkyl)amino; perfluoro(C₁-C₁₈)alkylthio; C₁-C₁₈alkylthio; C₁-C₁₈ acetyl; C₃-C₁₀ cycloalkyl; C₃-C₁₀ cycloalkoxy; or astraight-chain or branched C₁-C₁₈ alkyl group that is mono-substitutedwith cyano, halo, or C₁-C₁₈ alkoxy, or poly-substituted with halo.

Additionally or alternatively, the substituents of the substitutedaromatic groups, substituted alicyclic groups and substitutedheterocyclic groups from which each of Q₁, Q₂, and Q₃ can be selected,can be further independently chosen from a group represented by one ofthe following formulas XIIIA and XIIIB,

-M(T)_((t-1))  XIIIA

-M(OT)_((t-1)),  XIIIB

With reference to Formulas XIIIA and XIIIB, M is chosen from aluminum,antimony, tantalum, titanium, zirconium and silicon, T is chosen fromorganofunctional radicals, organofunctional hydrocarbon radicals,aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, and tis the valence of M.

Liquid crystal mesogens from which each of Q_(q), Q₂, and Q₃ can each beindependently selected, include but are not limited to art-recognizedliquid crystal mesogens. With some embodiments, the liquid crystalmesogens can be selected from those described in United States PatentApplication Publication No. US 2009/0323011 A1, see paragraphs [0052] to[0095] and Table 1, the disclosure of which is incorporated herein byreference in their entirety.

With further reference to Formula XIII, the _(s)ubs_(c)ripts c, d, e,and f are each independently chosen from an integer ranging from 1 to20, inclusive of the upper and lower limits (e.g., from 2 to 15, or from3 to 10).

The S₁, S₂, S₃, S₄, and S₅ groups of Formula XIII are each independentlychose from a spacer unit. The spacer unit can in each case beindependently chosen from, —(CH₂)_(g)—, —(CF₂)_(h)—, —Si(CH₂)_(g)—,—Si(CH₃)₂O)_(h)—, in which g is independently chosen for each occurrencefrom 1 to 20, and h is a whole number from 1 to 16 inclusive.Alternatively, or additionally, the spacer unit can be independentlychosen from —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)—C(Z′)—, or a singlebond, in which Z is independently chosen for each occurrence fromhydrogen, C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl and aryl, and Z′ isindependently chosen for each occurrence from C₁-C₁₈ alkyl, C₃-C₁₀cycloalkyl and aryl. Further alternatively, or additionally, the spacerunit can be independently chosen from —O—, —C(O)—, —C≡C—, —N═N—, —S—,—S(O)—, —S(O)(O)—, —(O)S(O)O—, —O(O)S(O)O—, or straight-chain orbranched C₁-C₂₄ alkylene residue, said C₁-C₂₄ alkylene residue beingunsubstituted, mono-substituted by cyano or halo, or poly-substituted byhalo.

With further reference to Formula XIII: when two spacer units comprisingheteroatoms are linked together, the spacer units are linked so thatheteroatoms are not directly linked to each other; each bond between S₁and Ring-A and S₁ and Ring-B is free of two heteroatoms linked together;and the bond between S₅ and P is free of two heteroatoms linked to eachother.

The P group of Formula XIII is chosen from, hydroxy, amino, C₂-C₁₈alkenyl, C₂-C₁₈ alkynyl, azido, silyl, siloxy, silylhydride,(tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato, thioisocyanato,acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl,2-(methacryloyloxy)ethylcarbamyl, aziridinyl, allyloxycarbonyloxy,epoxy, carboxylic acid, carboxylic ester, acryloylamino,methacryloylamino, aminocarbonyl, C₁-C₁₈ alkyl aminocarbonyl,aminocarbonyl(C₁-C₁₈)alkyl, C₁-C₁₈ alkyloxycarbonyloxy, halocarbonyl,hydrogen, aryl, hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,amino(C₁-C₁₈)alkyl, C₁-C₁₈ alkylamino, di-(C₁-C₁₈)alkylamino, C₁-C₁₈alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈ alkoxy(C₁-C₁₈)alkoxy, nitro,poly(C₁-C₁₈)alkyl ether, (C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl,polyethyleneoxy, polypropyleneoxy, ethylenyl, acryloyl,acryloyloxy(C₁-C₁₈)alkyl, methacryloyl, methacryloyloxy(C₁-C₁₈)alkyl,2-chloroacryloyl, 2-phenylacryloyl, acryloyloxyphenyl,2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxetanyl,glycidyl, cyano, isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinylether, vinyl ester, a styrene derivative, main-chain and side-chainliquid crystal polymers, siloxane derivatives, ethyleneiminederivatives, maleic acid derivatives, fumaric acid derivatives,unsubstituted cinnamic acid derivatives, cinnamic acid derivatives thatare substituted with at least one of methyl, methoxy, cyano and halogen,or substituted or unsubstituted chiral or non-chiral monovalent ordivalent groups chosen from steroid radicals, terpenoid radicals,alkaloid radicals and mixtures thereof. The substituents of the groupsfrom which P can be selected are independently chosen from C₁-C₁₈ alkyl,C₁-C₁₈ alkoxy, amino, C₃-C₁₀ cycloalkyl, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy,fluoro(C₁-C₁₈)alkyl, cyano, cyano(C₁-C₁₈)alkyl, cyano(C₁-C₁₈)alkoxy ormixtures thereof. With some embodiment P can be a structure having from2 to 4 reactive groups. With further embodiments, P can be anunsubstituted or substituted ring opening metathesis polymerizationprecursor.

With further reference to Formula XIII, subscripts d′, e′ and f′ areeach independently chosen from 0, 1, 2, 3, and 4, provided that the sumof d′+e′+f′ is at least 1.

With some embodiments of the present invention, Ring-A and Ring-B areeach independently selected from unsubstituted and substituted arylgroups, such as unsubstituted and substituted phenyl groups.Correspondingly, in accordance with some embodiments of the presentinvention, the compound represented by Formula I, is more particularlyrepresented by the following Formula Ia.

With reference to Formula Ia, m, n, R¹, R², R³, R⁴ and R⁵ are each asdescribed previously herein. The compound represented by Formula Ia canbe referred to as an indeno-fused naphtho-compound, such as anindeno-fused naphthol (e.g., when R⁵ is hydrogen).

In accordance with some embodiments of the present invention, theunsaturated compound represented by Formula II, can be represented bythe following Formula IIb.

With reference to Formula IIb, m, R¹, R³ and R¹⁶ are each as describedpreviously herein. The unsaturated compound represented by Formula IIbcan be referred to as an unsaturated indanone acid/ester compound, or anindenone acid/ester compound (depending on whether R¹⁶ is hydrogen, oran optionally substituted hydrocarbyl group). With the unsaturatedcompound represented by Formulas II, IIa (protected with an oxazolinegroup) or IIb, in some embodiments of the present invention: R¹ for eachm is independently selected from C₁-C₆ alkyl, C₃-C₇ cycloalkyl, C₁-C₈haloalkyl, fluoro, chloro, and —O—R₁₀′; R³ is selected from hydrogen,C₁-C₈ alkyl, C₁-C₈ haloalkyl, and C₃-C₇ cycloalkyl; and R¹⁶ is selectedfrom hydrogen and C₁-C₈ alkyl.

The saturated compound represented by Formula IV, in some embodiments,is represented by the following Formula IVb.

With reference to Formula IVb, m, R¹, R³, R⁴ and R¹⁶ are each asdescribed previously herein. The saturated compound represented byFormula IVb can be referred to as a saturated indenone acid/estercompound, or an indanone acid/ester compound (depending on whether R¹⁶is hydrogen, or an optionally substituted hydrocarbyl group).

The second nucleophile represented by Formula V, in some embodiments, isrepresented by the following Formula Va.

With reference to Formula Va, m, R² and M² are each as describedpreviously herein.

The substituted intermediate represented by at least one of Formulas VI,VII and VII, are each in some embodiments represented by the followingFormulas VIb, VIIb and VIIIb.

With Formulas VIb, VIIb and VIIIb, m, n, R¹, R², R³ and R⁴ are each asdescribed previously herein.

The A and B ring fused indenopyran compound represented by Formula XV isin some embodiments represented by the following Formula XVa.

With the indeno-fused ring pyran compound represented by Formula XVa, m,n, R¹, R², R³ and R⁴ are each as described previously herein. The B andB′ groups of the indeno-fused ring pyran compound represented by FormulaXVa are each as described previously and further herein. Theindeno-fused ring pyran compound represented by Formula XVa can bereferred to an indeno-fused naphthopyran compound.

The B and B′ groups of, for example, the indeno-fused ring pyrancompound represented by Formulas XV and XVa, and the propargyl alcoholrepresented by Formula XVI, are described in further detail as follows.More particularly, B and B′ can each independently be selected from: anaryl group that is mono-substituted with a reactive substituent or acompatiblizing substituent; a substituted phenyl; a substituted aryl; asubstituted 9-julolindinyl; a substituted heteroaromatic group chosenfrom pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl,carbazoyl, benzopyridyl, indolinyl, and fluorenyl. The phenyl, aryl,9-julolindinyl, or heteroaromatic substituents are selected from: areactive substituent R; an unsubstituted, mono-, di-, or tri-substitutedphenyl or aryl group; 9-julolidinyl; or an unsubstituted, mono- ordi-substituted heteroaromatic group chosen from pyridyl, furanyl,benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,benzopyridyl, indolinyl, and fluorenyl.

The phenyl, aryl and heteroaromatic substituents (i.e., the substituentsof the substituted phenyl, aryl and heteroaromatic groups) of the B andB′ groups can each be independently selected from: hydroxyl, a group—C(═O)R₂₁, wherein R₂₁ is —OR₂₂, —N(R₂₃)R₂₄, piperidino, or morpholino,wherein R₂₂ is allyl, C₁-C₂₀ alkyl, phenyl, mono(C₁-C₂₀)alkylsubstituted phenyl, mono(C₁-C₂₀)alkoxy substituted phenyl,phenyl(C₁-C₂₀)alkyl, mono(C₁-C₂₀)alkyl substituted phenyl(C₁-C₂₀)alkyl,mono(C₁-C₂₀)alkoxy substituted phenyl(C₁-C₂₀)alkyl, C₁-C₂₀alkoxy(C₂-C₂₀)alkyl or C₁-C₂₀ haloalkyl, R₂₃ and R₂₄ are eachindependently C₁-C₂₀ alkyl, C₅-C₁₀ cycloalkyl, phenyl or substitutedphenyl, the phenyl substituents being C₁-C₂₀ alkyl or C₁-C₂₀ alkoxy, andsaid halo substituent is chloro or fluoro, aryl, mono(C₁-C₂₀)alkoxyaryl,di(C₁-C₂₀)alkoxyaryl, mono(C₁-C₂₀)alkylaryl, di(C₁-C₂₀)alkylaryl,haloaryl, C₃-C₁₀ cycloalkylaryl, C₃-C₁₀ cycloalkyl, C₃-C₁₀cycloalkyloxy, C₃-C₁₀ cycloalkyloxy(C₁-C₂₀)alkyl, C₃-C₁₀cycloalkyloxy(C₁-C₂₀)alkoxy, aryl(C₁-C₂₀)alkyl, aryl(C₁-C₂₀)alkoxy,aryloxy, aryloxy(C₁-C₂₀)alkyl, aryloxy(C₁-C₂₀)alkoxy, mono- ordi(C₁-C₂₀)alkylaryl(C₁-C₂₀)alkyl, mono- ordi-(C₁-C₂₀)alkoxyaryl(C₁-C₂₀)alkyl, mono- ordi-(C₁-C₂₀)alkylaryl(C₁-C₂₀)alkoxy, mono- ordi-(C₁-C₂₀)alkoxyaryl(C₁-C₂₀)alkoxy, amino, mono- ordi-(C₁-C₂₀)alkylamino, diarylamino, piperazino,N-(C₁-C₂₀)alkylpiperazino, N-arylpiperazino, aziridino, indolino,piperidino, morpholino, thiomorpholino, tetrahydroquinolino,tetrahydroisoquinolino, pyrrolidyl, C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl,C₁-C₂₀ alkoxy, mono(C₁-C₂₀)alkoxy(C₁-C₂₀)alkyl, acryloxy, methacryloxy,or halogen.

The B and B′ groups can also each independently be an unsubstituted ormono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl,imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl, andacridinyl, each of said substituents being C₁-C₂₀ alkyl (e.g., C₁-C₁₂alkyl), C₁-C₂₀ alkoxy (e.g., C₁-C₁₂ alkoxy), phenyl, or halogen.

In addition, the B and B′ groups can each be independently selected froma group represented by the following general Formulas XIVA or XIVB,

Independently with each of general formulas XIVA and XIVB, K is —CH₂— or—O—, and M is —O— or substituted nitrogen, provided that when M issubstituted nitrogen, K is —CH₂—, the substituted nitrogen substituentsbeing hydrogen, C₁-C₂₀ alkyl, or C₁-C₂₀ acyl, each R₂₅ beingindependently chosen for each occurrence from C₁-C₂₀ alkyl, C₁-C₂₀alkoxy, hydroxyl, and halogen, R₂₆ and R₂₇ each being independentlyhydrogen or C₁-C₂₀ alkyl, and u is an integer ranging from 0 to 2.

Each B and B′ group can independently be a group represented by thefollowing general Formula XXVIII,

With the group represented by general Formula XXVIII, R₂₈ is hydrogen orC₁-C₁₂ alkyl, and R₂₉ is an unsubstituted, mono- or di-substituted groupchosen from naphthyl, phenyl, furanyl, and thienyl. The substitutents ofthe mono- or di-substituted naphthyls, phenyls, furanyls, and thienyls,are in each case independently selected from C₁-C₁₂ alkyl, C₁-C₁₂alkoxy, or halogen.

The B and B′ groups can together form a member selected from, afluoren-9-ylidene, a mono-substituted fluoren-9-ylidene, or adi-substituted fluoren-9-ylidene. The substituents of themono-substituted fluoren-9-ylidene, and the di-substitutedfluoren-9-ylidene can in each case be independently selected from C₁-C₂₀alkyl (e.g., C₁-C₁₂ alkyl), C₁-C₂₀ alkoxy (e.g., C₁-C₁₂ alkoxy), orhalogen.

With some embodiments of the present invention, with the A and B ringfused indenopyran compound, for example, represented by Formulas XV andXva: R¹ for each m, and R² for each n, are in each case independentlyselected from C₁-C₆ alkyl, C₃-C₇ cycloalkyl, C₁-C₈ haloalkyl, fluoro,chloro, and —O—R₁₀′; R³ and R⁴ are each independently selected fromhydrogen, C₁-C₈ alkyl, C₁-C₈ haloalkyl, and C₃-C₇ cycloalkyl; and B andB′ are each independently selected from aryl (e.g., phenyl) substitutedwith C₁-C₆ alkoxy, and aryl (e.g., phenyl) substituted with morpholino.

With some embodiments of the present invention, B and B′ can each beindependently selected from polyalkoxy, and polyalkoxy having apolymerizable group. The polyalkoxy, and polyalkoxy having apolymerizable group from which B and B′ can each be independentlyselected can be represented by the following Formulas XXVI and XXVII.

—Z[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]Z′  XXVI

—[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]Z′  XXVII

With Formulas XXVI and XXVII, —Z is chosen from —C(O)— or —CH₂—, Z′ ischosen from C₁-C₃ alkoxy or a polymerizable group. As used herein and inthe claims, the term “polymerizable group” means any functional groupcapable of participating in a polymerization reaction.

With some embodiments, polymerization of the polymerizable indeno-fusedring pyran compounds, such as polymerizable indeno-fused naphthopyrans,can occur by mechanisms described with regard to the definition of“polymerization” in Hawley's Condensed Chemical Dictionary, ThirteenthEdition, 1997, John Wiley & Sons, pages 901-902. Those mechanismsinclude: by “addition,” in which free radicals are the initiating agentsthat react with the ethylenically unsaturated double bond of the monomerby adding to it on one side at the same time producing a new freeelectron on the other side; by “condensation,” involving the splittingout of a component, such as water molecules, by two reacting monomers;and by so-called “oxidative coupling.”

Examples of polymerizable groups include, but are not limited to,hydroxy, thiol, isocyanate groups, oxirane groups (e.g.,oxiranylmethyl), radically polymerizable ethylenically unsaturatedgroups, allyl groups, (meth)acryloxy, and 2-(methacryloxy)ethylcarbamyl.When there are 2 or more polymerizable groups on the indeno-fused ringpyran compound, they can be the same or different.

With some embodiments and with further reference to Formulas XXVI andXXVII: the group, —(OC₂H₄)_(x)—, can represent poly(ethylene oxide); thegroup —(OC₃H₆)_(y)—, can represent poly(propylene oxide); and the group—(OC₄H₈)_(z)—, can represent poly(butylene oxide). When used incombination, the poly(ethylene oxide), poly(propylene oxide) andpoly(butylene oxide) groups of Formulas XXVI and XXVII can be in arandom or block order within the polyalkoxy moiety. The subscriptletters x, y and z of Formulas XXVI and XXVII are each independently anumber between 0 and 50, and the sum of x, y and z is between 2 and 50.The sum of x, y and z can be any number that falls within the range of 2to 50 (e.g., 2, 3, 4 . . . 50). This sum can also range from any lowernumber to any higher number within the range of 2 to 50 (e.g., 6 to 50,31 to 50). The numbers for x, y, and z are average values and can bepartial numbers (e.g., 9.5).

As previously discussed, some of the groups of the various compounds andintermediates described herein, such as each of the R¹, R², R³, R⁴, Band B′ groups, can independently be selected from or include at leastone of a reactive substituent and/or a compatiblizing substituent. Ifthe various compounds and/or intermediates described previously herein,such as the indeno-fused ring compound represented by Formula I, theunsaturated compound represented by Formula II, and/or the indeno-fusedring pyran compound represented by Formula XV, include multiple reactivesubstituents and/or multiple compatiblizing substituents, each reactivesubstituent and each compatiblizing substituent can be independentlychosen.

The reactive substituent and the compatibilizing substituent can eachindependently be represented in each case by one of:

-A′-D-E-G-J  (XVII);

-A′-D-J  (XVIII);

-A′-G-J  (XIX);

-G-E-G-J  (XX);

-D-G-J  (XXI);

-G-J  (XXII);

and

-D-E-G-J  (XXIII);

-D-J  (XXIV);

-A′-J  (XXV).

With formulas (XVII) through (XXV), non-limiting examples of groups that-A′- can represent according to various non-limiting embodimentsdisclosed herein include —O—, —C(═O)—, —CH₂—, —OC(═)— and —NHC(═O)—,provided that if -A′- represents —O—, -A′- forms at least one bond with-J.

Non-limiting examples of groups that -D- can represent according tovarious non-limiting embodiments include a diamine residue, wherein afirst amino nitrogen of said diamine residue can form a bond with -A′-,or a substituent or an available position on the compound (such as theindeno-fused naphthol or indeno-fused naphthopyran), and a second aminonitrogen of said diamine residue can form a bond with -E-, -G- or -J;and an amino alcohol residue, wherein an amino nitrogen of the aminoalcohol residue can form a bond with -A′-, or a substituent or anavailable position on the compound (such as the indeno-fused naphthol orindeno-fused naphthopyran), and an alcohol oxygen of said amino alcoholresidue can form a bond with -E-, -G- or -J. Alternatively, according tovarious non-limiting embodiments disclosed herein the amino nitrogen ofsaid amino alcohol residue can form a bond with -E-, -G- or -J, and saidalcohol oxygen of said amino alcohol residue can form a bond with -A′-,or a substituent or an available position on the compound (such as the Aand B ring fused inden-6-ol compound or A and B ring fused indenopyrancompound).

Non-limiting examples of suitable diamine residues that -D- canrepresent include an aliphatic diamine residue, a cyclo aliphaticdiamine residue, a diazacycloalkane residue, an azacyclo aliphatic amineresidue, a diazacrown ether residue, and an aromatic diamine residue.Specific non-limiting examples diamine residues that can be used inconjunction with various non-limiting embodiments disclosed hereininclude the following:

Non-limiting examples of suitable amino alcohol residues that -D- canrepresent include an aliphatic amino alcohol residue, a cyclo aliphaticamino alcohol residue, an azacyclo aliphatic alcohol residue, adiazacyclo aliphatic alcohol residue and an aromatic amino alcoholresidue. Specific non-limiting examples amino alcohol residues that canbe used in conjunction with various non-limiting embodiments disclosedherein include the following:

With continued reference to formulas (XVII) through (XXV) above,according to various non-limiting embodiments disclosed herein, -E- canrepresent a dicarboxylic acid residue, wherein a first carbonyl group ofsaid dicarboxylic acid residue can form a bond with -G- or -D-, and asecond carbonyl group of said dicarboxylic acid residue can form a bondwith -G-. Non-limiting examples of suitable dicarboxylic acid residuesthat -E- can represent include an aliphatic dicarboxylic acid residue, acycloaliphatic dicarboxylic acid residue and an aromatic dicarboxylicacid residue. Specific non-limiting examples of dicarboxylic acidresidues that can be used in conjunction with various non-limitingembodiments disclosed herein include the following:

According to various non-limiting embodiments disclosed herein, -G- canrepresent a group —[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]—O—, wherein x, yand z are each independently chosen and range from 0 to 50, and a sum ofx, y, and z ranges from 1 to 50; a polyol residue, wherein a firstpolyol oxygen of said polyol residue can form a bond with -A′-, -D-,-E-, or a substituent or an available position on the indeno-fusednaphthopyran, and a second polyol oxygen of said polyol can form a bondwith -E- or -J; or a combination thereof, wherein the first polyoloxygen of the polyol residue forms a bond with a group—[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]— (i.e., to form the group—[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]—O—), and the second polyol oxygenforms a bond with -E- or -J. Non-limiting examples of suitable polyolresidues that -G- can represent include an aliphatic polyol residue, acyclo aliphatic polyol residue and an aromatic polyol residue.

More particularly, illustrative and non-limiting examples of polyolsfrom which the polyol residues that -G- can represent can be formedaccording to various non-limiting embodiments disclosed herein include:(a) low molecular weight polyols having an average molecular weight lessthan 500, such as, but not limited to, those set forth in U.S. Pat. No.6,555,028 at col. 4, lines 48-50, and col. 4, line 55 to col. 6, line 5,which disclosure is hereby specifically incorporated by referenceherein; (b) polyester polyols, such as, but not limited to, those setforth in U.S. Pat. No. 6,555,028 at col. 5, lines 7-33, which disclosureis hereby specifically incorporated by reference herein; (c) polyetherpolyols, such as but not limited to those set forth in U.S. Pat. No.6,555,028 at col. 5, lines 34-50, which disclosure is herebyspecifically incorporated by reference herein; (d) amide-containingpolyols, such as, but not limited to, those set forth in U.S. Pat. No.6,555,028 at col. 5, lines 51-62, which disclosure is herebyspecifically incorporated by reference; (e) epoxy polyols, such as, butnot limited to, those set forth in U.S. Pat. No. 6,555,028 at col. 5line 63 to col. 6, line 3, which disclosure is hereby specificallyincorporated by reference herein; (f) polyhydric polyvinyl alcohols,such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028at col. 6, lines 4-12, which disclosure is hereby specificallyincorporated by reference herein; (g) urethane polyols, such as, but notlimited to those set forth in U.S. Pat. No. 6,555,028 at col. 6, lines13-43, which disclosure is hereby specifically incorporated by referenceherein; (h) polyacrylic polyols, such as, but not limited to those setforth in U.S. Pat. No. 6,555,028 at col. 6, lines 43 to col. 7, line 40,which disclosure is hereby specifically incorporated by referenceherein; (i) polycarbonate polyols, such as, but not limited to, thoseset forth in U.S. Pat. No. 6,555,028 at col. 7, lines 41-55, whichdisclosure is hereby specifically incorporated by reference herein; and(j) mixtures of such polyols.

With further reference to formulas (XVII) through (XXV), according tovarious non-limiting embodiments disclosed herein, -J can represent agroup -K, wherein -K represents a group such as, but not limited to,—CH₂COOH, —CH(CH₃)COOH, —C(O)(CH₂)_(w)COOH, —C₆H₄SO₃H, —C₅H₁₀SO₃H,—C₄H₈SO₃H, —C₃H₆SO₃H, —C₂H₄SO₃H and —SO₃H, wherein “w” ranges from 1 to18. According to other non-limiting embodiments -J can representhydrogen that forms a bond with an oxygen or a nitrogen of linking groupto form a reactive moiety such as —OH or —NH. For example, according tovarious non-limiting embodiments disclosed herein, -J can representhydrogen, provided that if -J represents hydrogen, -J is bonded to anoxygen of -D- or -G-, or a nitrogen of -D-.

According to still further non-limiting embodiments, -J can represent agroup -L or residue thereof, wherein -L can represent a reactive moiety.For example, according to various non-limiting embodiments disclosedherein -L can represent a group such as, but not limited to, acryl,methacryl, crotyl, 2-(methacryloxy)ethylcarbamyl,2-(methacryloxy)ethoxycarbonyl, 4-vinylphenyl, vinyl, 1-chlorovinyl orepoxy. As used herein, the terms acryl, methacryl, crotyl,2-(methacryloxy)ethylcarbamyl, 2-(methacryloxy)ethoxycarbonyl,4-vinylphenyl, vinyl, 1-chlorovinyl, and epoxy refer to the followingstructures:

As previously discussed, -G- can represent a residue of a polyol, whichis defined herein to include hydroxy-containing carbohydrates, such asthose set forth in U.S. Pat. No. 6,555,028 at col. 7, line 56 to col. 8,line 17, which disclosure is hereby specifically incorporated byreference herein. The polyol residue can be formed, for example andwithout limitation herein, by the reaction of one or more of the polyolhydroxyl groups with a precursor of -A′-, such as a carboxylic acid or amethylene halide, a precursor of polyalkoxylated group, such aspolyalkylene glycol, or a hydroxyl substituent of the A and B ring fusedindenopyran compound. The polyol can be represented by q-(OH)_(a) andthe residue of the polyol can be represented by the formula—O-q-(OH)_(a-1), wherein q is the backbone or main chain of thepolyhydroxy compound and “a” is at least 2.

Further, as discussed above, one or more of the polyol oxygens of -G-can form a bond with -J (i.e., forming the group -G-J). For example,although not limiting herein, wherein the reactive and/or compatiblizingsubstituent comprises the group -G-J, if -G- represents a polyol residueand -J represents a group -K that contains a carboxyl terminating group,-G-J can be produced by reacting one or more polyol hydroxyl groups toform the group -K (for example as discussed with respect to Reactions Band C at col. 13, line 22 to col. 16, line 15 of U.S. Pat. No.6,555,028, which disclosure is hereby specifically incorporated byreference herein) to produce a carboxylated polyol residue.Alternatively, if -J represents a group -K that contains a sulfo orsulfono terminating group, although not limiting herein, -G-J can beproduced by acidic condensation of one or more of the polyol hydroxylgroups with HOC₆H4SO₃H; HOC₅H₁₀SO₃H; HOC₄H₈SO₃ H; HOC₃H₆SO₃H;HOC₂H₄SO₃H; or H₂SO₄, respectively. Further, although not limitingherein, if -G- represents a polyol residue and -J represents a group -Lchosen from acryl, methacryl, 2-(methacryloxy)ethylcarbamyl and epoxy,-L can be added by condensation of the polyol residue with acryloylchloride, methacryloyl chloride, 2-isocyanatoethyl methacrylate orepichlorohydrin, respectively.

The A and B ring fused indenopyran compounds prepared by the methods ofthe present invention, can be used to render compositions and/orarticles photochromic. Examples of articles that can be renderedphotochromic by the indeno-fused ring pyran compounds of the presentinvention include, but are not limited to, optical elements, displays,windows (or transparencies), mirrors, and components or elements ofliquid crystal cells. As used herein the term “optical” means pertainingto or associated with light and/or vision. Examples of optical elementsthat can be rendered photochromic include, without limitation,ophthalmic elements, display elements, windows, mirrors, and liquidcrystal cell elements. As used herein the term “ophthalmic” meanspertaining to or associated with the eye and vision. Non-limitingexamples of ophthalmic elements include corrective and non-correctivelenses, including single vision or multi-vision lenses, which can beeither segmented or non-segmented multi-vision lenses (such as, but notlimited to, bifocal lenses, trifocal lenses and progressive lenses), aswell as other elements used to correct, protect, or enhance(cosmetically or otherwise) vision, including without limitation,magnifying lenses, protective lenses, visors, goggles, as well as,lenses for optical instruments (for example, cameras and telescopes). Asused herein the term “display” means the visible or machine-readablerepresentation of information in words, numbers, symbols, designs ordrawings. Non-limiting examples of display elements include screens,monitors, and security elements, such as security marks. As used hereinthe term “window” means an aperture adapted to permit the transmissionof radiation there-through. Non-limiting examples of windows includeautomotive and aircraft transparencies, windshields, filters, shutters,and optical switches. As used herein the term “mirror” means a surfacethat specularly reflects a large fraction of incident light. As usedherein the term “liquid crystal cell” refers to a structure containing aliquid crystal material that is capable of being ordered. Onenon-limiting example of a liquid crystal cell element is a liquidcrystal display.

Articles can be rendered photochromic with the indeno-fused ring pyrancompounds of the present invention by methods including, but not limitedto, imbibition methods, cast-in-place methods, coating methods, in-moldcoating methods, over-mold methods, and lamination methods. Withimbibition methods, the indeno-fused ring pyran compound is typicallydiffused into a polymeric material of a previously formed or fabricatedarticle, such as a substrate or previously applied coating or film.Imbibition can be performed by immersing the polymeric material of apreviously formed or fabricated article in a solution containing the Aand B ring fused indenopyran compound, with or without heating.Thereafter, although not required, the A and B ring fused indenopyrancompound can be bonded with the polymeric material (e.g., of thesubstrate or coating).

With cast-in-place methods, the A and B ring fused indenopyran compoundcan be mixed with: a polymer and/or oligomer composition in solution ormelt form; or monomer composition in liquid form, so as to form acastable photochromic composition. The castable photochromic compositionis then typically introduced into the cavity of a mold (e.g., a lensmold). The castable photochromic composition is then set (e.g., cured)within the mold so as to form a photochromic article.

With articles that include a substrate, the A and B ring fusedindenopyran compounds of the present invention can be connected to atleast a portion of the substrate as part of a coating that is connectedto at least a portion of the substrate. The substrate can be a polymericsubstrate or an inorganic substrate (such as, but not limited to, aglass substrate). The A and B ring fused indenopyran compound of thepresent invention can be incorporated into at least a portion of acoating composition prior to application of the coating composition tothe substrate. Alternatively, a coating composition can be applied tothe substrate, at least partially set, and thereafter the A and B ringfused indenopyran compound of the present invention can be imbibed intoat least a portion of the coating. As used herein, the terms “set” and“setting” include, without limitation, curing, polymerizing,cross-linking, cooling, and drying.

Photochromic articles can be prepared using the A and B ring fusedindenopyran compounds of the present invention by art-recognized in-moldcoating (or in-mold casting) methods. With in-mold coating methods, aphotochromic coating composition including the A and B ring fusedindenopyran compound of the present invention, which can be a liquidcoating composition or a powder coating composition, is applied to atleast a portion of the interior surface of a mold, and then at leastpartially set. Thereafter, a polymer solution or melt, or oligomeric ormonomeric solution or mixture is cast or molded within the mold cavityand in contact with the previously applied photochromic coatingcomposition, and at least partially set. The resulting photochromicarticle is then removed from the mold. Non-limiting examples of powdercoatings in which the A and B ring fused indenopyran compounds accordingto various non-limiting embodiments disclosed herein can be employed areset forth in U.S. Pat. No. 6,068,797 at col. 7, line 50 to col. 19, line42, which disclosure is hereby specifically incorporated by referenceherein.

Photochromic articles prepared using the A and B ring fused indenopyrancompounds of the present invention can also be formed by art-recognizedover-mold methods. Over-mold methods typically involve forming asubstrate within a mold, and then forming an interior space between thesubstrate and an interior surface of the mold, into which a photochromiccoating composition is then subsequently introduced (e.g., injected) andthen set (e.g., cured). Alternatively, over-mold methods can involveintroducing a previously formed substrate into a mold, such that aninterior space is defined between the substrate and an interior moldsurface, and thereafter a photochromic coating composition is introduced(e.g., injected) into the interior space.

Photochromic articles, prepared using the A and B ring fused indenopyrancompounds prepared by the methods of the present invention, can also beformed by art-recognized lamination methods. With lamination methods, afilm comprising the A and B ring fused indenopyran compounds of thepresent invention can be adhered or otherwise connect to a portion ofthe substrate, with or without an adhesive and/or the application ofheat and pressure. Thereafter, if desired, a second substrate can beapplied over the first substrate and the two substrates can be laminatedtogether (e.g., by the application of heat and pressure) to form anelement wherein the film comprising the A and B ring fused indenopyrancompound is interposed between the two substrates. Methods of formingfilms comprising a photochromic material can include for example andwithout limitation, combining a photochromic material with a polymericsolution or oligomeric solution or mixture, casting or extruding a filmtherefrom, and, if required, at least partially setting the film.Additionally or alternatively, a film can be formed (with or without aphotochromic material) and imbibed with the photochromic material.

The A and B ring fused indenopyran compounds prepared by the methods ofthe present invention, can be used alone or in combination with otherphotochromic materials. Classes of photochromic materials that can beused in combination (e.g., in mixture) with the A and B ring fusedindenopyran compounds of the present invention include, but are notlimited to: spiro(indoline)naphthoxazines andspiro(indoline)benzoxazines, for example as described in U.S. Pat. Nos.3,562,172, 3,578,602, 4,215,010, 4,342,668, 5,405,958, 4,637,698,4,931,219, 4,816,584, 4,880,667, and 4,818,096; benzopyrans, for exampleas described in U.S. Pat. Nos. 3,567,605, 4,826,977, 5,066,818,4,826,977, 5,066,818, 5,466,398, 5,384,077, 5,238,931, and 5,274,132;photochromic organo-metal dithizonates, such as, (arylazo)-thioformicarylhydrazidates, e.g., mercury dithizonates which are described in, forexample, U.S. Pat. No. 3,361,706; and fulgides and fulgimides, e.g., the3-furyl and 3-thienyl fulgides and fulgimides which are described inU.S. Pat. No. 4,931,220 at column 20, line 5 through column 21, line 38.

The present invention is more particularly described in the followingexamples, which are intended to be illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art. Unless otherwise specified, all parts and all percentagesare by weight.

EXAMPLES

In Part 1 of the Examples, the synthesis procedures used to make thenaphthols and photochromic materials according to various non-limitingembodiments disclosed herein are set forth in Examples 1-4 and IA-4A.Part 2 describes the photochromic performance testing and results forphotochromic compounds of Examples 2A-4A.

Example 1

Step 1

A mixture of 4-bromoacetophenone (148 g), dimethyl succinic ester (130g) and toluene (2.5 L) was mechanically stirred in a reaction flask.Potassium t-butoxide (100 g) was added in one portion. A yellow colorwas observed and a lot of precipitate formed. One hour later, water (1L) was added. The water layer was collected and washed with toluene (200mL) twice. It was then acidified to pH 3 using 12 N HCl and extractedwith ethyl acetate (1 L). The ethyl acetate solution was collected,dried over magnesium sulfate and concentrated. To the resulting viscousmixture, hexane (1 L) was added. A large amount of oil precipitated outand then crystallized. After filtration, white crystals (170 g) wereobtained as the product. NMR showed that the product had a structureconsistent with (E)-4-(4-bromophenyl)-3-(methoxycarbonyl)pent-3-enoicacid.

Step 2

The product of Step 1 (160 g) was mixed with 50% sodium hydroxide watersolution (200 g) and water (4 liters) in a four liter beaker. Themixture was heated to boil. After one hour, the mixture was cooled toroom temperature and the pH of the mixture was adjusted to 2 using 12 NHCl. The precipitated off-white crystals were collected by filtrationand dried to yield 152 grams of product. NMR showed that the product hada structure consistent with (E)-2-(1-(4-bromophenyl)ethylidene)succinicacid.

Step 3

A mixture of the product of Step 2 (152 g), DBSA (5 g) and toluene (1 L)was heated up to reflux with water removed by a Dean-Stark trap. After 2hours, the mixture was cooled to room temperature and then passedthrough a silica gel plug column using 2/8 ethyl acetate/hexanes as theeluent. After concentration, oil was obtained. To the oil, hexanes (1 L)was added and the product crystallized out. It was collected byfiltration and dried in vacuum to yield off-white crystals (130 grams)as the product. NMR showed that the product had a structure consistentwith (E)-3-(1-(4-bromophenyl)ethylidene)dihydrofuran-2,5-dione.

Step 4

To a stirred mixture of the aluminum chloride (130 g) and methylenechloride (1 L), the product of Step 3 (125 g) was added in threeportions in 5 minutes. After stirring at room temperature for 2 hours,the reaction mixture was poured into water (2 L) slowly. THF (1 L) andsolid sodium chloride (100 g) was then added to the mixture. Theresulting water layer was removed by a separatory funnel. The recoveredorganic layer was dried over magnesium sulfate and concentrated. Ethylacetate (200 ml) was added and the resulting yellow crystals werecollected and dried to yield 50 grams of product. NMR showed that theproduct had a structure consistent with2-(6-bromo-3-methyl-1-oxo-1H-inden-2-yl)acetic acid.

Step 5

A mixture of manganese chloride (7.46 g) and lithium chloride (5 g) wasdried at 200° C. in a vacuum oven for an hour. Under the protection ofnitrogen, THF was added (200 ml) and the mixture was stirred for 30minutes until a clear solution was obtained. To the solution, copper (I)chloride (0.59 g) and the product of Step 4 (19.4 g) were added. Themixture was stirred until clear and then cooled to 0° C. To the mixture,2M THF solution of butyl magnesium bromide (99 ml) was added dropwise.The reaction mixture turned black eventually with the addition of moreBuMgBr. The addition was completed in 2 hours. After the addition, themixture was stirred at 0° C. for 2 hours and then quenched using water(200 mL). The pH of the mixture was adjusted to ˜2 using 12 N HCl. Ethylacetate (200 mL) was added. The resulting organic portion was collectedby a separatory funnel, dried, and concentrated. The product waspurified by CombiFlash® Rf from Teledyne ISCO to yield oil (4 g) as theproduct. NMR showed that the product had a structure consistent with2-(5-bromo-1-butyl-1-methyl-3-oxo-2,3-dihydro-1H-inden-2-yl)acetic acid.

Step 6

Under the protection of nitrogen, solid magnesium (1.1 g) was placed ina dried reaction flask. THF (60 mL) and 1-bromo-4-trifluoromethylbenzene(10.3 g) was added. The mixture was stirred at room temperature. Icebath was used occasionally to control the reaction temperature to aboutroom temperature. After two hours the resulting Grignard solution wastransferred to a dropping funnel that was attached to another driedreaction flask, in which a mixture of anhydrous THF (300 ml), anhydrouslanthanum chloride (11.3 g) and anhydrous lithium chloride (5.8 g) wasstirred until clear. The product of Step 5 (3.9 g) was added to theflask. The resulting mixture was stirred for 10 minutes at roomtemperature and then cooled in an ice bath. The Grignard in the droppingfunnel was added into the stirred reaction mixture over 10 minutes andthe mixture was stirred at room temperature for 4 hours.

The reaction was stopped by the addition of water (100 mL). The pH wasadjusted to 2 using 12 N HCl. Ethyl acetate was added (100 mL). Theresulting organic phase was collected by a separatory funnel, washedwith NaCl/water, dried over magnesium sulfate and concentrated.

The recovered oil was re-dissolved in toluene (100 mL) in a reactionflask. Acetic anhydride (10 grams) and bismuth triflate (0.04 g) wereadded. The mixture was refluxed for 2 hours and cooled to roomtemperature. Methanol (100 mL) and 12 N HCl (1 mL) were added. Themixture was refluxed for 12 hours and then concentrated. The crudeproduct was purified by silica gel plug column separation using 2/8ethyl acetate/hexane as the eluent. Oil (3 g) was obtained as theproduct. NMR showed that the product had a structure consistent with10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol.

Example 1A

The product of Example 1 (3 g) was placed in a reaction flask. To theflask, 1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol (2.1g), 1,2-dichloroethane (30 ml) and p-toluenesulfonic acid (70 mg) wasadded. The mixture was refluxed for 4 hours, concentrated and passedthrough a silica gel plug column using 2/8 ethyl acetate/hexane as thesolvent. A brownish oil (2 grams) was obtained as the product. NMRshowed that the product had a structure consistent with3-(4-fluorophenyl)-3-(4-(N-morpholino)phenyl)-10-bromo-6-trifluoromethyl-13-methyl-13-butyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 2

The procedures from Example 1 were followed except that: in Step 5, 1.4M THF solution of methyl magnesium bromide was used in place of butylmagnesium bromide; in Step 6, 1-bromo-4-trifluoromethoxybenzene was usedin place of 1-bromo-4-trifluoromethylbenzene. NMR showed that theproduct had a structure consistent with10-bromo-7,7-dimethyl-3-(trifluoromethoxy)-7H-benzo[c]fluoren-5-ol.

Example 2A

The procedures from Example 1A were followed except that the product ofExample 2 was used in place of the product of Example 1 and1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol. NMR showedthat the product had a structure consistent with3,3-bis(4-methoxyphenyl)-10-bromo-6-trifluoromethoxy-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 3

The procedures from Example 1 were followed except that in Step 6,1-bromo-4-fluorobenzene was used in place of1-bromo-4-trifluoromethylbenzene. NMR showed that the product had astructure consistent with10-bromo-7-butyl-3-fluoro-7-methyl-7H-benzo[c]fluoren-5-ol.

Example 3A

The procedures from Example 1A were followed except that the product ofExample 3 was used in place of the product of Example 1 and1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol. NMR showedthat the product had a structure consistent with3,3-bis(4-methoxyphenyl)-10-bromo-6-fluoro-13-methyl-13-butyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 4

The procedures from Example 1 were followed except that in Step 6,1-bromo-3,5-difluorobenzene was used in place of1-bromo-4-trifluoromethylbenzene. NMR showed that the product had astructure consistent with10-bromo-7-butyl-2,4-difluoro-7-methyl-7H-benzo[c]fluoren-5-ol.

Example 4A

The procedures from Example 1A were followed except that the product ofExample 4 was used in place of the product of Example 1 and1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol. NMR showedthat the product had a structure consistent with3,3-bis(4-methoxyphenyl)-10-bromo-5,7-fluoro-13-methyl-13-butyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Part 2: Photochromic Performance Testing and Results

The photochromic performance of the photochromic materials of Examples2A-4A were tested as follows. A quantity of the photochromic material tobe tested, calculated to yield a 1.5×10⁻³ M solution, was added to aflask containing 50 grams of a monomer blend of 4 parts ethoxylatedbisphenol A dimethacrylate (BPS 2EO DMA), 1 part poly(ethylene glycol)600 dimethacrylate, and 0.033 weight percent 2,2′-azobis(2-methylpropionitrile) (AlBN). The photochromic material was dissolved into themonomer blend by stirring and gentle heating if necessary. After a clearsolution was obtained, it was vacuum degassed before being poured into aflat sheet mold having the interior dimensions of 2.2 mm×6 inches (15.24cm)×6 inches (15.24 cm). The mold was sealed and placed in a horizontalairflow, programmable oven programmed to increase the temperature from40° C. to 95° C. over a 5 hour interval, hold the temperature at 95° C.for 3 hours and then lower it to 60° C. for over a 2 hour interval.After the mold was opened, the polymer sheet was cut using a utilityknife to score the surface and snap into 2 inch (5.1 cm) test squares.

The photochromic test squares prepared as described above were testedfor photochromic response on an optical bench. Prior to testing on theoptical bench, the photochromic test squares were exposed to 365 nmultraviolet light for about 15 minutes to cause the photochromicmaterial to transform from the ground state-form to an activated-stateform, and then placed in a 75° C. oven for about 15 minutes to allow thephotochromic material to revert back to the ground state-form. The testsquares were then cooled to room temperature, exposed to fluorescentroom lighting for at least 2 hours, and then kept covered (that is, in adark environment) for at least 2 hours prior to testing on an opticalbench maintained at 73° F. (23° C.).

The optical bench fitted with a Schott 3 mm KG-2 band-pass filter,neutral density filter(s) and a Newport Model #67005 300-watt Xenon arclamp with Model #69911 power supply in association with a Newport Model689456 Digital Exposure/Timer was used to control the intensity of theirradiance beam utilized for activation of the sample. A Uniblitz model#CS25S3ZM0 with model #VMM-D3 controller) high-speed computer controlledshutter, a fused silica condensing lens for beam collimation of thisactivation lamp beam though a quartz glass water bath sample chamber.

A custom made broadband light source for monitoring responsemeasurements was directed through the sample such that the angle betweenthe activation source and the monitoring beam is 30 degrees with thesample positioned perpendicular to this monitoring beam. This broad beamlight source is obtained by collecting and combining separately filteredlight from a 100-Watt tungsten halogen lamp (controlled by a LambdaUP60-14 constant voltage powder supply) with a split-end, bifurcatedfiber optical cable to enhance the short wavelength light intensity.After passing through the sample, this monitoring light was refocusedinto a 2-inch integrating sphere and fed to an Ocean Optics S2000spectrophotometer by fiber optic cables. Ocean Optics SpectraSuite andPPG proprietary software were used to measure response and control theoperation of the optical bench.

The λmax-vis is the wavelength in the visible spectrum at which themaximum absorption of the activated-state form of the photochromiccompound in a test square occurs. The λmax-vis wavelength was determinedby testing the photochromic test squares in a Varian Cary 4000UV-Visible spectrophotometer; it may also be calculated from thespectrum obtained by the S2000 spectrometer on the optical bench.

The change in Optical density at saturation for each test sample wasdetermined by opening the shutter from the xenon lamp and measuring thetransmittance after exposing the test chip to 3 W/m2 UVA radiation for30 minutes. The change in Optical density at saturation was calculatedusing the formula: ΔOD=log (% Tb/% Ta), where % Tb is the percenttransmittance in the bleached state, % Ta is the percent transmittancein the activated state both at the λmax-vis and the logarithm is to thebase 10. The first fade half life (“T½”) or bleach rate is the timeinterval in seconds for the absorbance of the activated-state form ofthe photochromic material in the test squares to reach one half the ΔODat saturation value at room temperature (23° C.), after removal of thesource of activating light. The Sensitivity (ΔOD/Min) is a measure ofhow quickly the sample darkens and is calculated from the equationΔODsen=ΔOD5min×12.

TABLE 1 Photochromic Performance Test Results Example # λ_(max-vis)Sensitivity ΔOD at T ½ (Compound #) (nm) (ΔOD/Min) saturation (sec) 2A572 0.44 0.27 35 3A 564 0.46 0.34 44 4A 551 0.65 0.44 35

The present invention has been described with reference to specificdetails of particular embodiments thereof. It is not intended that suchdetails be regarded as limitations upon the scope of the inventionexcept insofar as and to the extent that they are included in theaccompanying claims.

We claim:
 1. An unsaturated compound represented by Formula II,

wherein Ring-A is selected from unsubstituted aryl, substituted aryl,unsubstituted fused ring aryl, substituted fused ring aryl,unsubstituted heteroaryl, and substituted heteroaryl, m is selected from0 to 4, R¹ for each m is independently selected from hydrocarbyloptionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—,—S(O)—, —SO₂—, —N═N—, —N(R₁₁′)— where R₁₁′ is selected from hydrogen,hydrocarbyl or substituted hydrocarbyl, —Si(OR₁₃′)_(k)(R₁₃′)_(j)—, wherek and j are each independently selected from 0 to 2, provided that thesum of k and j is 2, and each R₁₃′ is independently selected fromhydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations oftwo or more thereof; substituted hydrocarbyl optionally interrupted withat least one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—,—N(R₁₁′)— where R₁₁′ is selected from hydrogen, hydrocarbyl orsubstituted hydrocarbyl, —Si(OR₁₃′)_(k)(R₁₃′)_(j)—, where k and j areeach independently selected from 0 to 2, provided that the sum of k andj is 2, and each R₁₃′ is independently selected from hydrogen,hydrocarbyl and substituted hydrocarbyl, and combinations of two or morethereof; cyano; and —N(R₁₁′)R₁₂′, wherein R₁₁′ and R₁₂′ are eachindependently selected from hydrogen, hydrocarbyl or substitutedhydrocarbyl, or R₁₁′ and R₁₂′ together form a ring structure optionallyincluding at least one heteroatom, and R³ is selected from hydrogen;hydrocarbyl optionally interrupted with at least one of —O—, —S—,—C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N═N—, and —N(R₁₁′)— where R₁₁′ isselected from hydrogen, hydrocarbyl or substituted hydrocarbyl, andcombinations of two or more thereof; and substituted hydrocarbyloptionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—,—S(O)—, —SO₂—, and —N(R₁₁′)— where R₁₁′ is selected from hydrogen,hydrocarbyl or substituted hydrocarbyl, and combinations of two or morethereof, and R¹⁶ is selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl.
 2. The unsaturated compound of claim 1, wherein, Ring-A isselected from unsubstituted aryl and substituted aryl; R¹ for each m isindependently selected from C₁-C₂₀ alkyl; C₃-C₁₀ cycloalkyl; substitutedor unsubstituted phenyl, the phenyl substituents being selected fromhydroxyl, halogen, carbonyl, C₁-C₂₀ alkoxycarbonyl, cyano,halo(C₁-C₂₀)alkyl, C₁-C₂₀ alkyl or C₁-C₂₀ alkoxy; —O—R₁₀′ or —(CO)—R₁₀′or —C(O)—OR₁₀′, wherein R₁₀′ is hydrogen, C₁-C₂₀ alkyl,phenyl(C₁-C₂₀)alkyl, mono(C₁-C₂₀)alkyl substituted phenyl(C₁-C₂₀)alkyl,mono(C₁-C₂₀)alkoxy substituted phenyl(C₁-C₂₀)alkyl,(C₁-C₂₀)alkoxy(C₂-C₂₀)alkyl, C₃-C₁₀ cycloalkyl, or mono(C₁-C₂₀)alkylsubstituted C₃-C₁₀ cycloalkyl; —N(R₁′)R₁₂′, wherein R₁₁′ and R₁₂′ areeach independently hydrogen, C₁-C₂₀ alkyl, phenyl, naphthyl, furanyl,benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl,fluorenyl, C₁-C₈ alkylaryl, C₃-C₁₀ cycloalkyl, C₄-C₂₀ bicycloalkyl,C₅-C₂₀ tricycloalkyl or C₁-C₂₀ alkoxyalkyl, wherein said aryl group isphenyl or naphthyl, or R₁₁′ and R₁₂′ come together with the nitrogenatom to form a C₃-C₂₀ hetero-bicycloalkyl ring or a C₄-C₂₀hetero-tricycloalkyl ring; a nitrogen containing ring represented by thefollowing graphic formula XIIA,

wherein each —Y— is independently chosen for each occurrence from —CH₂—,—CH(R₁₃′) —, —C(R₁₃′)₂—, —CH(aryl)-, —C(aryl)₂-, and —C(R₁₃′)(aryl)-,and Z is —Y—, —O—, —S—, —S(O)—, —SO₂—, —NH—, —N(R₁₃′)—, or —N(aryl)-,wherein each R₁₃′ is independently C₁-C₆ alkyl, each aryl isindependently phenyl or naphthyl, m is an integer 1, 2 or 3, and p is aninteger 0, 1, 2, or 3 and provided that when p is 0, Z is —Y—; a grouprepresented by one of the following graphic formulae XIIB or XIIC,

wherein R₁₅, R₁₆, and R₁₇ are each independently hydrogen, C₁-C₂₀ alkyl,phenyl, or naphthyl, or the groups R₁₅ and R₁₆ together form a ring of 5to 8 carbon atoms and each R^(d) is independently for each occurrenceselected from C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, fluoro or chloro, and Q is aninteger 0, 1, 2, or 3; and unsubstituted, mono-, or di-substitutedC₄-C₁₈ spirobicyclic amine, or unsubstituted, mono-, and di-substitutedC₄-C₁₈ spirotricyclic amine, wherein said substituents are independentlyaryl, C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, or phenyl(C₁-C₂₀)alkyl; or twoadjacent R¹ groups, or two adjacent R² groups, independently togetherform a group represented by one of XIID and XIIE:

wherein T and T′ are each independently oxygen or the group —NR₁₁′—,wherein R₁₁′, R₁₅, and R₁₆ are as set forth above; and R³ is selectedfrom, (i) hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, C₃-C₁₀ cycloalkyl,allyl, benzyl, or mono-substituted benzyl, said benzyl substituentsbeing chosen from halogen, C₁-C₂₀ alkyl or C₁-C₂₀ alkoxy; (ii) anunsubstituted, mono- di- or tri-substituted group chosen from phenyl,naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl,thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, orindolyl, said group substituents in being chosen from halogen, C₁-C₂₀alkyl or C₁-C₂₀ alkoxy; (iii) mono-substituted phenyl, said substituentlocated at the para position being —(CH₂)_(t)— or —O—(CH₂)_(t)—, whereint is the integer 1, 2, 3, 4, 5 or 6, said substituent being connected toan aryl group which is a member of a photochromic material; (iv) thegroup —CH(R¹⁰)G, wherein R¹⁰ is hydrogen, C₁-C₆ alkyl or theunsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl,and G is —CH₂OR¹¹, wherein R¹¹ is hydrogen, —C(O)R¹⁰, C₁-C₂₀ alkyl,C₁-C₂₀ alkoxy(C₁-C₂₀)alkyl, phenyl(C₁-C₂₀)alkyl, mono(C₁-C₂₀)alkoxysubstituted phenyl(C₁-C₂₀)alkyl, or the unsubstituted, mono- ordi-substituted aryl groups phenyl or naphthyl, each of said phenyl andnaphthyl group substituents being C₁-C₂₀ alkyl or C₁-C₂₀ alkoxy.
 3. Theunsaturated compound of claim 2, wherein, R¹ for each m is independentlyselected from C₁-C₆ alkyl, C₃-C₇ cycloalkyl, C₁-C₈ haloalkyl, and—O—R₁₀′, R³ is selected from hydrogen, C₁-C₈ alkyl, C₁-C₈ haloalkyl, andC₃-C₇ cycloalkyl, and R¹⁶ is selected from hydrogen and C₁-C₈ alkyl. 4.The unsaturated compound of claim 1, wherein said unsaturated compoundis represented by Formula IIb,